Organic Syntheses Based on Name Reactions
Organic Syntheses Based on Name Reactions A Practical Guide to 750 Transformations
Third Edition
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Foreword by D. Seebach
Organic Syntheses Based on Name Reactions When studying chemistry at the Technische Hochschule Karlsruhe, more than 50 years
ago, we had tomemorize close to 50 Name Reactions for the final examination in organic chem-
istry. The then one and only book on Name Reactions was Krauch-Kunz’s Reaktionen der Organischen Chemie, which tried to be complete at the time. In the mean time, synthetic organic
methodology has experienced an explosive expansion, which is due to two fundamentally dif-
ferent types of developments: (i) the classical reactions have been modified to become regio-,
diastereo-, and enantioselective, and to become catalytic (cf. organocatalysis). (ii) The—mostly
catalytic—use of transition-metal derivatives has enriched organic synthesis with new types of reactions (cf. metathesis), which can almost all be rendered enantioselective by employing
chiral ligands on the metal centers. Many of the resulting procedures for carrying out certain
transformations have turned out to be of broad scope and to be generally reliable, so that—for
brevity—they were named after their inventor(s) in synthetic discussions, and that’s all about
Name Reactions. It is, therefore, not surprising that several monographs on this subject have
appeared and that new editions of books on Name Reactions are essential.
This book first appeared in 1994, a second edition in 2002, and now the third one in 2011,
with the number of Name Reactions covered increasing from ca. 450 to 550 to over 700, and the
number of cited papers from 2100 to 3300 to over 6000. Still, the size of the volume(s) remained
“manageable.” Of course, the authors had to make, with a personal bias, decisions about which
reactions to include and which to replace (an evolutionary process!). In fact, when browsing
through the three editions, one can get the impression that they are quite different books, in
spite of the common unique features, which are, first of all, a typical specific experimental pro-
cedure and a proposal of a mechanistic course for the covered Name Reaction. Then, there are
updated references to most recent publications and cross-references to similar transformations
with a different name; the quality of the formulae has greatly improved; there are most useful
indices of names, reagents, reactions, abbreviations, and group transformations; last but not
least, there is a new, larger section entitled “An Overview of Synthesis-Related Name Reac-
tion,” listing, for instance, all Name Reactions, in which aldol-type transformations; cycload-
ditions; or S, Se, Si, Sn, Bi compounds are involved, to name only three of the 40 entries in this
section. A scientific book without an excellent index for access to its content is not a good book;
this one is, indeed, excellent, not least because of these indices!
I went through the pages of this third edition with great pleasure. I learned about some trans-
formations, which were new to me. To some extent, it was a learning experience like when I
studied a textbook as a student. The book has, indeed, textbook character and could be used in
lab courses as a “cook book” and in advanced organic chemistry courses for problem-solving
sessions and as a source of exam questions—without requesting that the students actually mem-
orize the Name Reactions, as in the old days: to cover the fundamental reactivities of organic
compounds they must learn names connected with some transformations, reagents, and mech-
anisms. On the other hand, a discussion between top synthetic organic chemists (cf. specialists
in total synthesis of complex natural products, “synthetic engineers”), with a life-long experi-
ence, will inevitably be full of reference to Name Reactions; when the name “pops up,” there is
immediate mutual understanding and agreement that there is mention of a generally applicable
and reliable chemical transformation.
In our time of online data bases, such as Chemical Abstract’s Scifinder, Beilstein/Gmelin’s
Reaxys (ReactionFlash), Houben-Weyl’s Science of Synthesis, or even Google and Wikipedia
(I have successfully tested some of the more “fancy” Name Reactions therein), it is appropriate
to ask the question: “Who needs a book on Name Reactions?” The above-mentioned unique features of the third edition of Organic Syntheses Based on Name Reactions will make sure
that many organic chemists in academia and in industry will want to have this book on their
shelves. The success of the second edition and the call for a third edition are evidence for this
view. Name Reactions are at the core of the art of organic synthesis!
Dieter Seebach ETH Zurich
Foreword by S. Danishefsky
What’s in a Name Reaction?—A Lot To my delight, I discovered that fascinating combination of rigor/hypothesis, hard-core the-
ory/intuition, and commercial-level practicality/artistic elegance known as organic chemistry
in a 1954 course at Yeshiva University. It was already clear that one of the challenges of Orgo
(particularly for the pre-meds) would be the systemization of a huge body of factual data, allow-
ing for retrieval of critical information at critical times (exams, etc.). Our official class textbook
was authored by Raymond Brewster at the University of Kansas. However, the achievers in the
course, whose ranks I sought to enter, also purchased a book written by Louis andMary Fieser at
Harvard. Though these two tomes actually covered a very similar body of chemistry, there were
some notable differences in style. Brewster attempted to rationalize the seemingly unmanage-
able collection of facts in Orgo under what was then a newly emerging theoretical construct,
encompassing mechanisms (still early days for “curved arrows”), effects of structure changes
on reactivity, and some of the then very new ideas regarding stereochemistry.
The Fiesers, in turn, placed heavier emphasis on analogy arguments. Fieser mechanisms in
those days tended to focus on proposed affinities between substrates and reactants with a high
premium on identifying likely leaving groups to be anticipated from various displacements
and condensations. Much of this line of mechanistic conjecture was captured in a “lasso-type”
presentation, wherein stable entities (cf. inter alia water, alcohols, amines, halides, etc.) were
extruded to drive otherwise mysterious processes forward.
More so than Brewster, the Fiesers utilized the medium of Name Reactions to facilitate dis-
course. The Name Reaction device in the Fiesers’ treatment tended to focus on overall reaction
phenomenology (addition, elimination, aliphatic substitution, aromatic substitution, cycloaddi-
tions, condensation, etc.) rather than on intimate goings on below the surface. Thus, for in-
stance, the Mannich Reaction would be seen as one which joined a secondary amine a to a
carbonyl group (at that time almost always a ketone) through one linking carbon (usually form-
aldehyde) by extrusion of water. With the explosive growth of the number of valuable reactions
in organic chemistry and with growing insights into mechanistic issues, the importance of
Name Reactions grew. The Name Reaction tended to embrace not only a transformation but
also a particular mechanistic idea. As such, Name Reactions facilitated discussions of both
mechanism and synthesis. Hence, the role of the Name Reaction classification in facilitating
discussion became central. Two people, more or less on the same structural and mechanistic
pages, could communicate a remarkable amount of information and even prospective ideas
through the use of well-chosen Name Reaction descriptors. Even today, I find Name Reactions
of increasingly great value in organizing my own thoughts about synthesis as well as mecha-
nisms, and in sketching out, if qualitatively, the landscape of our science.
In principle, it might have been argued that the need for this type of classification is decreas-
ing in the face of powerful searching technology for canvassing large bodies of information,
including structures, and even reaction types. Surely no one could argue that, in this day
and age, the medium of the Name Reaction is the primary way of conveying descriptive
and mechanistic information. However, the Name Reaction system is still a major aid in
classifying large amounts of information in digestible form. As a classroom teacher, mastery of
the key Name Reactions is high up on my list of charges to the class on day one of the course.
Accordingly, I was very pleased to respond to the invitation of Professor Alfred Hassner to
comment on his emerging book, which updates, in a most valuable way, an increasing number
of Name Reactions. Even 57 years after taking the course described above, I remain totally ex-
cited at the concept of the awesome power of chemical synthesis. The notion that any structure
(within reason!), of which the human mind can conceive, is a possible target for chemical syn-
thesis remains to me one of the most noble ideas in the epistemology of science. The time is long
since past when triumphs in synthesis are viewed primarily as personalized mountain climbing
exercises. The macho/bravado element is still there, as it is in all artistry-intensive human un-
dertaking but is far less central. Synthesis is really about the capacity of the human imagination
and human resourcefulness to find ways of joining molecules in a precise, disciplined way with
high levels of control. Many of these molecules are of immediate interest from a material sci-
ence or pharmaceutical perspective. Others are of interest as probes for evaluating hypotheses
in structure theory or in biological signal transduction cascades. Aside from its intrinsic appeal
to the artistic impulse, synthesis plays an important role in human progress.
The opportunity of dedicating one’s intellectual imagination to complex problems, many of
which are apt to serve the needs of a growingly needful society, must be seen as a great priv-
ilege. The means for codifying information, which is central in this regard, while rewarding the
initiators (even posthumously) of what becomes a Name Reaction retains its special cultural
status in assisting the forward march of our science. Name Reaction assignments have about
them a significant element of intellectual history. However (and needless to say), the tracing
back of all the antecedents of an idea is actually an endless process. What Name Reactions
are really about is an agreed upon vocabulary, by convention, for communicating concepts
in concise but human terms, befitting one of the most esthetics-intensive of scientific activities,
that is, organic synthesis.
Not surprisingly, with the growing complexity and urgency of problems with which a sci-
entist is faced comes an increasing need for multidisciplinary ventures. I would argue (though
not without an admittedly strong dose of field chauvinism) that the truly unique gift that chem-
istry brings to such urgent collaborations is its aspiration for achieving unencumbered synthe-
sis. This expansiveness distinguishes chemical synthesis from the unbelievably powerful (more
circumscribed) engine of biosynthesis. Melding the skill sets of biology-mediated synthesis and
unencumbered chemical synthesis is one of the great opportunities at the chemistry/biology
frontier.
While it is well to think about issues of abstract logic and strategy, and ways in which they
influence chemical synthesis, the actual drivers of the field are the huge advances in reaction
feasibility arising from fundamental studies of methodology and its enabling mechanisms. In
short, the often unsung heroes of the awesome triumphs in chemical synthesis are the subjects of
these Name Reactions (not to speak of their students and postdocs!).
I am pleased to congratulate my friend and field colleague, Fred Hassner, and his coauthor
Irishi Namboothiri. They surely need have no doubt that this latest book on Name Reactions
will be read in a continuing way and with great pleasure by their fellow scientists/artists.
Sam Danishefsky Columbia University
x Foreword by S. Danishefsky
Preface to the Third Edition
The past 10 years, since the publication of the successful second edition of Organic Syntheses Based on Name Reactions, have witnessed a renaissance in organic synthesis; especially in the discovery of new reagents and chiral catalysts that have spurned development of asymmetric
syntheses. This has made possible the synthesis of a significant number of complex natural
products in an enantioselective manner. In the process one continues to notice that many syn-
thetic methods, reagents, and reactions are being referred to in the organic chemistry research
community by the names of their discoverers or developers.
The proliferation of published material in chemical journals has led to journal requirements
that authors be more succinct in their publications (witness the fact of extensive Supplemental
Material in many journals); hence one often sees procedures or methods referred to by Name
rather than by lengthy explanations. For the student of organic chemistry, there is the advantage
of mnemonic that some prefer.
One of the comments on the second edition of Organic Syntheses Based on Name Reactions was that we omitted some older and less utilized Name Reactions that had appeared in the first
edition. Hence for the sake of being comprehensive, we decided to keep such Name Reactions
in this revision. Further, we have added over 100 new Name Reactions, the choice of which, of
course, reflects our own bias, and for that we apologize.
All reactions have been brought up to date by including recent references where available. If
possible, we have consulted living authors about their Name Reaction. In some cases, no recent
references were found, and this may reflect the fact that more modern or simpler reactions are
now preferred.
It appears that people hesitate to refer to reactions by name if they bearmore than two or three
names. This made it desirable to break up reactions such as Hunsdiecker–Borodin–Cristol–
Firth–Kochi into the more natural Hunsdiecker (Ag salts of RCOOH), Cristol–Firth (HgO
and RCOOH), and Kochi (Pb derivatives). Similarly, in some cases, we separated a Name Re-
action from its asymmetric variant, such as the Michael addition or Diels–Alder reaction, in
order to avoid them being too cumbersome. Even so, since there are now several asymmetric
catalysts known for the same reaction, lumping all together would be quite unwieldy. Further,
we felt it was relevant to finally give credit to major contributions of chemists who developed
such well-established reactions as free radical dehalogenation with Bu3SnH (now Kuivila–
Beckwith) or carbodiimide coupling reagents (now Sheehan). Ionic liquids and their asymmet-
ric version are also included. It will be noticed that quite a few name reactions are related to well
known reactions (Friedel–Crafts, aldol, Michael, Grignard) but are known by different names.
Some reactions are often known by one name but can also be referred to by another name,
and this we tried to reflect in the introductory statement by including the other names as
well; for instance, Grob Fragmentation also known as Grob–Eschenmoser, or Fokin
Cu-catalyzed Click reaction also known as Fokin–Sharpless–Meldal, or Hunsdiecker also
known as Hunsdiecker–Borodin.
There is always a big problem combining the chemistry described by the originator of a
Name Reaction with the chemistry developed later and further adjusting it into limited space.
Obviously, after the original publication, the reaction has sometimes mutated to quite a differ-
ent animal.
The Overview section is a new and very important feature to the third edition. For instance,
the Overview lists syntheses of olefins by CþC bond formation (over 16 Name Reactions) or by
elimination (over 30 Names). This is not only useful for advanced organic chemistry students,
but should be very valuable to the researcher as at a glance comparisons of related methods for
synthesis of particular functional groups are provided. Details can then be found under the
names. Other Overview sections include asymmetric syntheses, syntheses of amine, cyclopro-
panes, 5- and 6-membered ring heterocyles and many more. Of course this is not meant as a
textbook and is limited to named reactions.
In addition the last few years have seen a proliferation of Pd- (and other metal-) catalyzed
coupling reactions; in fact several Nobel prizes were awarded in this field. We have therefore
also included a brief Overview of Pd catalyzed Name Reactions with a general reaction pathway.
Wherever possible in the new edition, we have alluded to the mechanism of reactions (prob-
able reaction pathway) by providing an intermediate or a description, yet leaving some freedom
for students to supplement details.
We limited the coverage of reactions since we preferred to keep the size and the cost of the
volume manageable.
The new addition maintains the successful format of providing important references (over
6000); in each case, this includes one of the first references to the reaction and a review ref-
erence (marked R) where available. Asymmetric syntheses are marked with an *. References
to books are generally not included. Further, a brief example of an experimental procedure is
provided in most cases. In the experimental, we often refer to “work up” which is usually meant
to include, where necessary, washing, drying, extraction, evaporation, and purification
(chromatography).
Important features of this monograph are the indexes, which should be helpful to the reader:
A name index with cross references to multiple names
A reagent index
A reaction index
A functional group transformation index, which allows one to search for conversions of one
functional group to another.
As well as a condensed Overview that includes, among others, aldol type reactions; asymmet- ric reactions; cyclopropanation; oxidations; rearrangements; S, Se, Si, Sn derivatives, etc. The Overview should prove valuable to the synthetic chemist as well as to students in universities,
when searching for or comparing procedures. In fact this format has led the second edition (even
without the Overview) to being adopted as a text in advanced organic chemistry courses.
We thank our families for their understanding during the extensive work on this book and are
grateful to Dr. Simcha Meir, Prashant Pavashe, Sundaram Rajkumar, and Mamta Dadwal for
their invaluable help in bringing this volume to fruition. Mistakes often creep in and we are
greatly indebted to Dr. Thomas Allmendinger and Mr. Simon Allmendinger for checking
the manuscript and suggesting corrections that had been overlooked. We are very grateful to
our editor Dr A. Shell for constant encouragement, suggestions as well as proofreading. This
monograph is dedicated to the memory of Cyd Hassner and of our children Suzie, Douglas and
Erica.
Preface to the Second Edition
The success of the first edition of “Organic Syntheses Based on Name Reactions and Unnamed Reactions” and the proliferation of new Name Reactions are the reason for this new revised
edition. It became obvious that many new reagents and reactions are being referred to in the
organic chemistry research community by their names. Hence, in addition to over 170 new re-
actions (previously referred to as Unnamed Reactions) in the first edition, we have included in
the second edition 157 new Name Reactions bringing the total to 545. However, we have elim-
inated the term “Unnamed Reactions” from the title of the monograph, since these reactions are
now no longer unnamed. Furthermore, we omitted some older and less utilized Name Reactions
that appeared in the first edition but have included them in the Name Index, by providing ref-
erence to the page number in the first edition (e.g. Baudisch 1-27, refers to first edition, p.27).
The new additions are all synthetically useful or not immediately obvious transformations.
In choosing them, emphasis was placed on stereoselective or regioselective reagents or reac-
tions including asymmetric syntheses. The latter are particularly timely with the recent Nobel
Prize in Chemistry awarded in this area.
Again we admit our own bias in choosing from the many interesting newer transformations
reported in the literature. Where possible we have tried to consult with the Name Reaction
major author. We apologize if inadvertently important reactions were omitted.
We have maintained the useful format of providing important references (over 3,300); in
each case this includes one of the first references to the reaction and a review reference where
available. Furthermore, an example of an experimental procedure is provided.
Important features of this monograph remain the indexes, which should be helpful to the
reader:
A reagent index; A reaction index, e.g. acylations, asymmetric synthesis; epoxidation, heteroannulations, re-
arrangements, etc.; as well as
A functional group transformation index, which allows one to search for conversions of one functional group to another. The latter has proved valuable to the synthetic chemist search-
ing for pathways to perform such synthetic procedures.
Hence, the monograph should be of interest to chemists in industry and academia. In fact this
format has led to the monograph being adopted as a text in advanced organic chemistry courses.
We thank our families for their understanding during the travail on this book and are grateful
to TEVA Pharmaceutical Co. for their support.
This monograph is dedicated to the memory of my dear wife Cyd (A.H.).
Alfred Hassner Carol Stumer
Non nova sed nove
Preface to the First Edition
And these are the names. . . The above are the opening words of Exodus, the second book of the Pentateuch. Already in
ancient times, names were important in association with events. As organic chemistry devel-
oped during the 20th century, researchers started associating synthetically useful reactions with
the names of discovers or developers of these reactions. In many cases such names serve merely
as a mnemonic, to remember a reaction more easily; there are few chemistry undergraduates
who do not know what the Friedel-Crafts reaction is.
In recent years there has been a proliferation of new reactions and reagents that have been so
useful in organic synthesis that often people refer to them by name. Many of these are stereo-
selective or regioselective methods. While the expert may know exactly what the Makosza vi-
carious nucleophilic substitution, or the Meyers asymmetric synthesis refers to, many students
as well as researchers would appreciate guidance regarding such “Name Reactions”.
It is in this context that we perceived the necessity to incorporate the older name reactions
with some newer name reactions or “unnamed reactions”, that are often associated with a name
but for which details, references and experimental details are not at everyone’s fingertips. This
was our inspiration for the current monograph “Organic Syntheses Based on Name Reactions and Unnamed Reactions”.
In particular, we thought it would be useful to include cross-references of functional group
transformations and an experimental procedure, so that the reader will be able to evaluate the
reaction conditions at a glance; for instance, is this reaction carried out at room temperature or at
200 C? For 1 h or 5 days? Are special catalysts required? How is the reaction worked up, what
yield can be expected?
The choice of which reactions to include is not an easy one. First there are the well known
“Name Reactions”, that have appeared in various monographs or in the old Merck index. Some
of these are so obvious mechanistically to the modern organic chemistry practitioner that we
have in fact omitted them; for instance, esterification of alcohols with acid chlorides – the
Schotten-Baumann procedure. Others are so important and so well entrenched by name, like
the Baeyer-Villiger ketone oxidation, that it is impossible to ignore them. In general, we have
kept older name reactions that are not obvious at first glance.
In some cases we have combined similar reactions under one heading, for instance, the
Hunsdiecker-Borodin-Cristol-Firth decarboxylative bromination. It is not a simple task to de-
cide whether credit is due to the first discoverer of a reaction or to its developers. Often an im-
provement on a method is more useful than the original discovery, and usually one reaction
owes its inception to some previous discovery; non nova sed nove. Except in the case of reactions that have been known for a long time under shared names, we
often took the liberty to include in the title, as well as in the references (here to save space), only
the name of the major author; for this we apologize to the co-authors, whose contributions are
often seminal. For reactions named after contemporary authors, we have tried to consult the
authors about choice of examples, etc. This led, for instance, to the Mannich-Eschenmoser
methylenation.
Among the newer reactions, we have chosen those that are not only synthetically useful,
but, at first glance, not immediately obvious transformations. Another criterion was the stereo-
chemical implication of the process. Yet, we admit our own bias in choosing from the plethora
of novel transformations that have appeared in the literature over the past 30 years or so. Space
limitation was by necessity a criterion. Nevertheless, we have included approximately 450
name reactions and 2100 references. We sincerely apologize if we have inadvertently omitted
important reactions.
In all cases we have tried to include the first reported reference, a reference to an experimen-
tal procedure, and whenever possible, a review reference (journal or Organic Reactions). In general, we did not include references to books, series of monographs, or toOrganic Syntheses; chemists will of course consult these where available.
Furthermore, we have compiled four indices, which should be helpful to the reader:
1. A names index with cross references to multiple names;
2. A reagents index; 3. An index to types of reactions, e.g. alkylations, stereoselective reductions, cyclizations,
etc.; and
4. Most important for the synthetic chemist is an index to the synthesis of functional groups, e.g., synthesis of alkenes from ketones, as well as conversion of ketones to alkenes.
We thank our families for their support and understanding during the travail on this book.
Special thanks are due to my son, Lawrence Hassner, for constructive suggestions and invalu-
able help.
We are grateful to the TEVA Pharmaceutical Co. for support of this project.
Alfred Hassner Carol Stumer
An Overview of Synthesis Related Name Reactions
This section lists all the name reactions according to the type of reaction, substrate involved or
product formed in the reaction.
Overview Sections:Acetylenes, allenes • Aldols • Aldol-type • Amines and N-derivatives • Amino acid, peptide • Asymmetric reactions • Boron compounds • C-Alkylation, acylation • Coupling C–C (Pd cat) • Coupling C–C (cat by other metals) • Coupling C–C miscellaneous • Coupling C¼O or C¼N with nucleophiles • Cyclizations (excludes heterocycles) • Cycload- ditions • Cyclopropane synthesis • Cyclopropane reactions • Epoxides • Fluorine compounds • Free radical reactions • Halogen compounds except F • Hydrogenation catalytic • N-Heterocy- cles synthesis 5-rings • Heterocycle of other 5-rings • N-Heterocycles synthesis 6-rings • Het- erocycles of other 6-rings • Heterocycles miscellaneous • Multicomponent reactions • Olefins via C þ C • Olefins via elimination • Oxidations • P, As-Compounds • Photochemical reac-
tions • Rearrangements • Rearrangements Sigmatropic • Reductions (excluding Pd catalytic
hydrogenation) • S-, Se-, Si- Sn-Compounds • Sugars, carbohydrates, nucleosides • Thermal
reactions.
Abbreviations Used:AA ¼ amino acid; acac ¼ acetoacetate; add ¼ addition; alc ¼ alcohol;
alkyl ¼ alkylation; aldeh ¼ aldehyde; arom ¼ aromatic, aromatization; asym ¼ asymmetric;
cat¼ catalyst, catalytic; cleav¼ cleavage; cond¼condensation; cpds¼ compounds; cyc¼ cycli-
zation; cycloadd¼ cycloaddition; degrade ¼ degradation; D–A¼ Diels–Alder; epox¼ epoxida-
tion, epoxide; equiv¼ equivalent; homol¼ homologation; oxid¼ oxidation; Pyr¼ pyridine; rad¼ free radical; reag¼ reagent; rearr¼ rearrangement; red¼ reduction; rx¼ reaction; sol¼ soluble;
synth ¼ synthesis; w ¼ with.
Acetylenes, Allenes: Bailey (cycloadd); Bergman (cycloarom); Berchtold (enamine
homol); Brown (alkyne isomeriz); Colvin (synth via diazo); Cooper–Finkbeiner (Mg propar-
gyl); Corey–Fuchs (synth from aldeh); Crabbe (allene synth); Doering–La Flamme (allenes);
Doetz (quinones from carbenes); Fokin (click, Cu cat); Fritsch–Buttenberg (alkyne synth);
Glaser–Sondheimer (alkyne coupling); Johnson (alkyne synth via F); Kinugasa (cycloadd);
Moore (cylobutenone coupling); Myers–Saito (cycloarom); Nicholas (propargyl alkyl Co);
Ohira–Bestmann (alkynes from aldeh); Pauson–Khand (Co cat CO rx); Reppe (acetylene
oligomer); Robinson (Michael–aldol annulation); Skattebol (allenes); Srebnik–Quntar
(cycloprop phosphonate); Stephen–Castro (cyclophane synth); Toste (alkyne Au cat); Whiting
(LAH red); Sonogashira (Pd, Cu coupling).
Aldol Reactions: Abiko–Masamune (asym aldol); Aldol (cond); Auwers (flavone synth);
Baer–Fischer (amino sugars via NO2–aldol); Baeyer–Drewson (indoxyl synth); Brown (anti- aldol); Camps (quinolinone synth); Chan–Brassard (acac equiv); Claisen (ester þ ester);
Claisen–Schmidt (ketone þ ald); Crimmins–Heathcock (anti-aldol); Enders (asym SAMP);
Erlenmeyer–Plochl (AA via hydantoin); Dieckmann (ester þ ester cyclization); Eschenmoser
(methylenation); Evans (chiral auxiliary); Evans–Mukaiyama (asym aldol); Fujimoto–Beleau
(ketone þ ketone); Friedlander (quinoline synth); Gold (aminomethylation); Hagemann ester
(cyclohexenone synth); Hajos–Parrish (asym Michael–aldol); Hanaoka–Wrobel (quinolizidine
synth); Henry (nitro aldol); Hiyama (amino acrylate synth); Houben–Hoesch (phenol
acylation); Kaiser–Johnson–Middleton (dinitrile cond); Lautens (aldol from vinylepoxides);
List-Barbas (asym aldol); Mannich (ketone þ iminium); Meldrum (aldol); Morita–Baylis–
Hillman (Michael–aldol); Mukaiyama (via Si enol ether); Ohira–Bestmann (alkyne from aldeh);
Rauhut (Michael–Michael); Robinson (annulation via Michael–aldol); Scholtz (pyridinyl ketone
þ aldehyde); Stobbe (succinic acid þ aldeh); Weiss–Cook (diketone annulation); Wilkes–
Armstrong (ionic liq, asym aldol); Wilkes–Rogers (ionic liq); Yamamoto (super Si double aldol);
Yonemitsu (3-component); Zeiss–Hassner (ketone transposition; Ziegler (dinitrile cond).
Aldol-type Reactions: Bally–Scholl (benzanthrone synth); Bouveault–Loquin (N¼O aldol);
Chichibabin (indolizidine synth); Claisen (ester þ ester); Darzens epoxide synth); Dieckmann
(cyclic Claisen); Doebner (malonic acid þ PhCH¼O); Duff (arom formylation); Ehrlich–Sachs
(via nitroso); Feist–Benary (furan synth); Ferrier (chiral cyclohexanone synth); Franchimond
(cyclobutanone synth); Garner (aldehyde rx); Gewald (aminothiophene synth); Gold (methylena-
tion); Granacher (arylpropanoic acid synth); Hinsberg (thiophene synth); Krische (hydroxyalky-
lation); Hagemann (acac to cyclohexenone); Hauser–Kraus (annulation); Hiyama (aminoacrylate
synth); Hooker (quinone rearr); Ivanov (Mg RCH2COOH alkyl); Knoevenagel (malonate þ PhCH¼O); Mander (carbethoxylation); Marschalck (aromatic þ CH2¼O); Passerini (isonitrile
þ aldeh); Perkin (Ac2Oþ PhCH¼O); Pinhey (arylation Pb); Prelog–Stoll (acyloin cond); Rathke
(b-ketoester synth); Reformatzky (Zn-ester þ ald); Roskamp (ketoester synth); Rovis–Enders
(asym Stetter cat); Schoelkopf (AA synth); Soderquist (asym allylation B); Stobbe (succinic acid
þ PhCH¼O); Szarvasy (carbethoxylation); Takei–Casiraghi (siloxy heterocycle þ aldeh); Vils-
meier (formylation); Williams–Ben–Ishai (AA synth); Wissner (HO-ketone synth); Wittig (ylide
þ aldehyde); Woodward (peptide synth); Zinke–Ziegler (calixarene synth).
Amine Synthesis (and N-Derivatives): Amadori (aminosugars synth); Angeli–Rimini
(hydroxamic acid synth); Baer–Fischer (amino sugar synth); Beller (aniline synth Pd);
Bertrand–Stephan (metal-free hydrogen via carbenes); Blum (aziridine synth); Borch (from
C¼O); von Braun (R3N degrad); Brown (via hydroboration); Bruylants (cyanoamine synth);
Buchwald–Hartwig (N-aryl-, N-vinylamine Pd); Chichibabin (aminopyr synth); Curtius (from
RCOOH); Darapski (COOEt to NH2); Davis (N-oxide synth); Davis–Ellmann (chiral sulfini-
mines); Delepine (RBr to amine); DeKimpe (aziridine, amidine synth); Dutt–Wormall (amine
to azide); Enders (asym synth); Eschweiler–Clark (amine methylation); Forster (diazo synth);
Forster–Decker (sec amine via imines); Frankel–Shibasaki (allylamine to enamine); Gabriel
(from alkyl halides); Garigipati (amidine synth); Girard (water sol hydrazones); Griess (deam-
ination); Hassner (aziridine, azirine synth); Hesse–Schmid (Zip amine expansion); Hill–Barrett
(cyclo hydroamination Ca cat); Hiyama (amino acrylate synth); Hoch–Campbell (aziridine
synth); Hofmann (amide degrad); Hofmann (isonitrile synth); Hofmann–Loeffler–Freytag
(amine cycl); Hofmann–Martius–Reilly–Hickinbottom (aniline rearr); Japp–Klimgemann
(hydrazone synth) Kabatchnik–Fields (aminophosphonate synth); Kaluza (isocyanate synth);
Katritzky (amines by pyridinium displacement); Kreszge (allyl amination); Lehn (N,
O-cryptants); Leuckart–Wallach (from C¼O); Lossen (hydroxamic to amine rearr); Mitsunobu
(O- to N-displacement); Mori–Shibasaki (from C¼OTi); Mundi (lactam to amine); Oleksyszyn
(amino phosphonic acid synth); Olofson (t-amine dealkylation); Petasis (3-component synth
B); Schweizer (allylamine synth); Schwartz (amine via hydrozirconation); Schwesinger
(N, P bases); Sharpless (allyl amination); Sheverdina–Kocheshkov (amines from cuprates);
Staudinger (via azide red); Stieglitz (N–Cl rearr); Strecker (AA synth); Suzuki (nitrile red
Co); Trost–Hassner (from azides w Li, Mg); Voight (amino ketone synth); Wakamatsu
(AA synth); Wasserman–Bormann (N-ring expansion); Wencker (aziridine synth); Zinner (hy-
droxylamine synth); Zard (rad aminomethylation).
Amino acids, Peptides, Amides: Beller (AA synth Pd); Bouveault–Loquin (AA via N¼O);
Bucherer–Bergs (AA via hydantoin); Darapski (cyanoacetate to AA); Erlenmeyer–Plochl
xviii An Overview of Synthesis Related Name Reactions
(AA via hydantoin); Granacher (AA from thioketo acid); Herbst–Engel (AA by transamina-
tion); Kabatchnik–Fields (aminophosphonate synth); Kagan–Horner–Knowles (AA from en-
amines Rh); Hiyama (amino acrylate synth); Honzl–Rudinger (peptide synth); Kotha–
Schoelkopf (AA from isocyanatoacetate); (Kowalski (b-AA from a-AA); Merrifield (via solid
phase); Milstein (amide from alcohol); O’Donnell (asym AA via glycine); Oleksyszyn (amino
phosphonic acid synth); Sanger (AA labeling); Schoelkopf (AA synth); Sheehan (EDC peptide
coupling); Staab (peptide via C¼O imidazole); Staudinger (via azide red); Strecker (AA synth);
Ugi (diamides, AA); Wakamatsu (AA from acetamide Co); Woodward (peptide synth);
Yamada (peptide synth).
Abramov (OH-phosphonate synth); Alder (ene rx); Barbas (Michael); Brown (anti-aldol); Brown (allylation); Brown (functional group synth); Brown (ketone red); Corey (ketone
red); Davies (Fe b-lactam auxiliary); Chan–Brassard (Si aldol); Corey (asym red); Crim-
mins–Heathcock (aldol); Evans (chiral auxiliary); Davis–Ellmann (chiral sulfinimines); Dutha-
ler–Hafner (allylation); Enders (SAMP); Evans (chiral aldol); Feringa–Pfaltz (asym Michael);
Ferrier (cyclohexanone synth); Garner (chiral aldehyde rxs); Hajos–Parrish (Michael–aldol);
Hassner–Ghera–Little (cyclopentanone synth); Hayashi–Uozumi (hydrosilation); Henry
(nitro-aldol); Hoffman–Yamamoto (B allylation); Hoppe (allylation); Jacobsen (epox synth
Mn); Julia–Colonna (epox via polyAA); List (Mannich); List-Barbas (asym aldol); Kagan–
Modena (sulfoxide synth); Katsuki (cyclopropane synth Zn, Al); Sharpless (epox Ti); Kinugasa
(nitrile oxide cycloadd); List-Barbas (aldol); List-MacMillan (dihydropyridine C¼C hydroge-
nation); Meldrum (aldol); Meyers (chiral oxazolines); Midland (propargyl ketone red); Mosher
(chirality determination); Mukaiyama (aldol via Si enol ether); Oppolzer (allyl alc); Oppolzer
(sultam); Pfaltz–Evans (bisoxazolines); Pfaltz–Feringa (asym Michael); Pirkle (resolution);
Roskamp (ketoester synth); Rovis–Enders (Stetter rx w chiral heterocycl carbene); Schoelkopf
(AA synth); Kotha–Schoelkopf (AA synth); Sharpless (dihydroxylation); Seebach (w chiral
oxazolidones); Seebach–Beck (TADDOL cat rxs); Shibasaki (cat heterobimetallic); Soderquist
(B-bicyclodecane); Stoltz (allylation); Strecker (AA synth); Takemoto (chiral thiourea cat);
Vasella–Bernet (cylopentane synth); Wilkes–Armstrong (ionic liq, chiral imidazolium);
Yamamoto (allylation); Yamamoto (allyl displacement).
Boron Compounds: Bertrand–Stephan (rx via carbenes); Brown (asym anti-aldol); Brown (asym allylation); Brown (asym ketone red); Brown (functional group synth); Brown (selective
red); Brown (ketone syn); Buchner–Curtius (homologation via carbene); Corey (asym red);
Liebeskind (thioester coupling via B); Matteson (aldeh synth via boronic ester); Oppolzer
(vinyl-B, Zn); Pasto–Matteson (B–C–Br rearr); Petasis (amine synth via B); Soderquist (bora-
bicycles); Suzuki–Miyaura (Pd coupling via B); Zeisel–Prey (ether cleav w BBr3).
C-Alkylation, Acylation: Baeyer (diarylmethane); Balson (aromatic alkylation Hþ); Blanc–Quellet (haloalkylation); Darzens–Nenitzescu (C¼C acylation); Eschenmoser (methy-
lenation); Friedel–Crafts (alkylation, acylation); Fries (phenol ester rearr); Lebedev (methox-
ymethylation); Mander (methoxycarbonylation); Mannich (b-aminoketone synth); Prins
(hydroxymethylation); Rieche (arom formylation Ti); von Richter (arom carboxylation);
Reimer–Tiemann (phenol formylation); Rosenmund–Braun (arom cyanation Cu); Rosini–
Bartoli (nitroarene alkylation via Mg); Stork–Huenig (cyanohydrin rxs); Szarvasy–Schopf
(methoxycarbonylation); Vilsmeier–Haack–Viehe (formylation); Yamazaki (arom cyanation);
Zinke–Suhl (cyclohexadienone from phenol).
Coupling C–C Pd Catalyzed: Beller (AA synth); Fukuyama (thioester to ketone); Fujiwara
(carboxylation); Heck–Fujiwara (alkene þ arom); Hiyama–DeShong–Denmark (silane þ aryl
halide); Kumada (via Mg); Larock (annulation); Liebeskind (thioester þ borane); Negishi (via
Zn, Al); Oppolzer (Pd, CO); Sonogashira (acetylenes Cu); Stille (ketone synth); Stille–Milstein
An Overview of Synthesis Related Name Reactions xix
(via Sn); Suzuki–Miyaura (via BR2); Trost (via trimethylenemethane); Tsuji–Trost (allylation);
Yamamoto (imine allylation).
Coupling C–C Catalyzed by Other Metals: Barbas (asym Michael); Barbier (Mg Sc);
Barton (Bi phenylation); Buchwald (Zr heterocycl); Burton (arom CF3 Cu); Collman (R-Br
þCO Fe); Davies (asymMichael Fe); DeMayo (2þ 2 photo); Doetz (Cr–COw alkyne); Dutha-
ler–Hafner (Ti allyl); Felkin (Mg ene); Feringa–Pfaltz (Cu–Zn asym Michael); Fuerstner (Fe
Mg); Fujiwara (Yb, La); Fukuyama (Zn keto synth); Friedel–Crafts (alkylation, acylation Al,
Sn, Ti); Gilman (via Li, Cu); Danheiser (w vinylsilane Ti); Gingras (triflate displace Sn); Gla-
ser–Sondheimer (Cu alkyne coupling); Grubbs (alkene–alkene metathesis Ru); Hollemann
(pinacol synth Mg Ti); Hoppe (allylation Ti); Kagan–Molander (R-I w C¼O or C¼C cycl
Sm); Kametani (RCH2NH2 to CN Cu O2); Kauffmann (dimerization Cu); Keck (rad allylation
Sn); Knochel (via Cu Zn); Kochi (via Fe Mg); Kulinkovich (cyclopropanol synth Ti Mg);
Krische (asym red coupling Rh, Ir); Ladenburg (pyr benzylation Cu); Larock (annulation Tl,
Pd); Liepa (V cycl); Lipshutz (cuprate add); Luche (Zn allylation); Michael (add); McMurry
(C¼O coupling Ti); Murahashi (Cu allylation); Nicholas (propargyl alkylation Co); Nugent–
Rajanbabu (epox Ti); Oppolzer (cyclopentenone w CO Pd); Pauson–Khand (cyclopentenone
w CO Co); Hollemann Pinacol (pinacol synth Mg CpTi, Mg Ti); Pinhey (arylation Pb); Reetz
(C¼O þ RTi); Reppe (acetylene Ni, Ti); Roelen (C¼C hydroformylation Co); Rosini–Bartoli
(NO2–arenes Mg); Sakurai–Hosomi (allylation, Si, Ti); Schwarz (via hydrozirconation);
Seebach–Beck (asym C¼O rx Ti, Mg); Soderquist (borabicycles); Srebnik–Quntar (cycloprop
phosphonate synth Zr); Takei–Casiraghi (siloxy heterocycl coupling Ti);Taylor–Ireland
(alcohol olefination Mn); Toste (acetylene rx Au); Ullmann (Ar–Ar Cu); Ullmann–Goldberg
(aromatic Cu, Zn); Wolfram–Schoernig–Hansdorf (oxidative carboxymethylation); Wurtz
(Na, Cu); Yamamoto (asym allyl displacement Cu).
Coupling C–CReactionsMiscellaneous:Alder (allylþC¼Oene rx);Alder–Rickert (D–A);
Alper (lactam from amine); Baeyer (diarylmethane Hþ); Baeyer–Villiger (arom tritylation);
Balaban–Nenitzescu–Prail (pyrylium salt synth); Bally–Scholl (benzanthrone synth);
Barbas (asym Michael); Bardhan–Sengupta (phenanthrene synth); Benary (formylation Mg);
Berchtold (enamine homologation); Blanc–Quellet (haloalkylation); Blomquist (macrocycle
synth); Bodroux–Chichibabin (o-formate to aldeh Mg); Boger (thermal cyclopentene synth);
Boger–Carboni (hetero D–A); Borsche–Beech (via arom diazonium); Bouveault (RLi formyla-
tion); Braverman–Mislow–Evans (sulfoxide rearr); Brown (ketone synth via boranes þ CO);
Brown (functional groups homologation via boranes þ S-ylides); Bruylants (allylamine synth);
Buchner–Curtius (homologation via diazo Rh); Cargill (cyclobutenyl ketone rearr); Carroll
(Claisen rearr); Chan (acyloxyacetate rearr); Claisen ([3,3] allyl enol ether rearr); Conia
(C¼O olefin ene rx); Cooper–Finkbeiner (alkene hydromagnesiation); Cope (3,3 diene rearr);
Darzens–Nenitzescu (C¼Cacylation);Dakin–West (RCOOHþAc2O);Danheiser (cyclopentene
synth via C¼CSi); Danishefsky (cyclohexenone synth via D–A); Davis–Ellmann (asym
sulfinimines); Demjanov (via alkyl diazonium); Dieckmann (ester–ester condens); Dowd (free
rad); Duff (aldeh synth); Emmert (pyridine Al–Hg); Enders (aldol via SAMP); Eschenmoser
(methylenation); Eschenmoser–Meerwein (acetamidation); Eschenmoser (episulfide contrac-
tion); Feringa–Pfaltz (asym Michael); Frankland (Hg, Zn); Freeman (Li DBB); Favorski
(a-haloketone rearr); Felkin (Mg ene); Fischer (indole); Fittig (pinacol rearr); Friedel–Crafts
(arom alkyl acyl); Fries (phenol ester rearr); Freund–Gustavson (cylopropane synth Zn);
Fritsch–Buttenberg (alkyne synth); Fuerstner (via Fe); Fugimoto–Belleau (keto aldol);
Garst–Spencer (furan synth);Gassman (oxindole synth);Gattermann–Koch (aromcarbonylation);
Gilman (via cuprates); Glaser–Sondheimer–Chodkiewicz (acetylene coupling); Gold
(methylenation); Gomberg–Bachmann–Graebe–Ulmann (via aryldiazonium); Grovenstein–
Zimmermann (carbanion rear); Hafner (azulene synth); Hammick (pyridine alkylation);
xx An Overview of Synthesis Related Name Reactions
Hass–Bender (C–Br to C¼O); Hassner–Ghera (cyclopentanation); Hauser–Beak (o-alkylation);
Hauser–Kraus (hydroquinones); Hoffman–Yamamoto (allylation, B, Sn); Hofmann–Martius
(C–C via aniline rearr); Houben–Hoesch (phenol acylation); Ireland (allyl ester 3.3 rearr); Ivanov
(via Grignard); Johnson (arom alkynylation F); Kauffmann (arene dimerization Cu); Kiliani–
Fischer (sugar homolog); Knunyants (F-alkyl); Koch–Haaf (carbocation carboxylation); Kotha–
Schoelkopf (AA via isonitriles); Kowalski (ester homolog); Kuivila–Beckwith (free rad C–C
formation); Kolbe (carboxylic acid electrolysis); Kolbe–Schmidt (salicylic acid synth); Liebig
(benzylic acid rearr); Johnson–Claisen (allyl orthoacetate rearr); Ladenburg ((pyridine alkyl);
Meisenheimer–Janovsky (arom acetone complex); Meldrum’s acid (aldol); Miller–Snyder (aryl
cyanides); Larock (annulation); Laszlo (via acid clay); Lebedev (methoxymethylation); Makosza
(arom substitution); Moore (cylobutenone coupling); Morita–Baylis–Hillman (Michael–aldol);
Mousseron–Fraisse–McCoy (cyclopropane from halo ester); Mundi (N-acyllactam rearr); Mura-
hashi (allylic alkylation Cu); Nokami (allyl alkylation); Parham (Li cycl) Paterno–Buchi (2 þ 2
addn); Parnes (Me transfer); Pauson–Khand (CO, Co); Perkin (malonate in cycl); Pedersen (imine
couplingNb); Prins–Kriewitz (olefin-carbocation); Pschorr (diazoniumþ arom); Rauhut–Currier
(Michael–Michael); Reformatsky (via haloester Zn); Rosenmund–Braun (Cu, cyanide); Reimer–
Tiemann (formylation); von Richter (aromatic acids syn); Rieche (formylation); Rovis–Enders
(asym Michael); Sakurai (Si allylation); Scholl (Al polyaromatic); Seebach–Beck (TADDOL
cat); Snieckus (o-alkylation); Soderquist (asym B-bicyclodecane); Stork–Hunig (cyanohydrin);
Stork (enamine rxs); Stork (radical cycl); Stork–Hauser (aminonitriles); Story (macrocycle synth);
Togni (trifluoromethyl); Torgov (enol allylation); Toste (Au catalyzed); Trost cyclopentanation;
Vasella–Bernet (cycloaddn); Wakamatsu (AA); Wilkes–Rogers (ionic liq); Williams–Ben–Ishai
(via enamide); Wolff (a-diazoketone rearr); Wilkes–Armstrong (ionic liq, D–A); Wolfram–
Schoernik (carboxymethylation); Woodward (peptide); Yamada (peptide); Zard (radical amino-
methylation); Ziegler (macrocycle); Zincke–Suhl (cyclohexadienone synth); Zinin (benzidine
rearrangement).
Coupling of C¼O or C¼N with C-Nucleophiles: (see also aldol-type reactions) Bailey
(diazabicyclooctanes synth); Barbier (in situ w Mg, In, Sc); Bargellini (3-component RCOOH
synth); Benzoin (condensation, Lapworth); Black (enol carbonate rearr); Blanc–Quellet (chlor-
oalkylation); Bodroux–Chichibabin (aldehydes from o-formates); Borsche–Beech ArN2 þ to
ArC¼O); Bouveault (arom formylation); Brown (anti-aldol); Bruylants (cyanoamine synth);
Chichibabin (arylpyridine from aldeh þ NH3); Collman (carbonylation, Fe); Colvin (alkyne
from ketone); Corey (epox from ketone); Corey–Fuchs (alkyne from aldeh P-ylide); Corey–
Seebach (dithiane nucleophile); Dakin–West (COOH to (C¼O)Me); Darzens (epoxide from
aldehþ haloester); De Kimpe (aldeh to aziridine); Dondoni (aldeh homologation); Duff (arom
aldeh from (CH2N)4); Duthaler–Hafner (allylation, Ti); Ehrlich–Sachs (aldeh via nitroso);
Emmert (C¼O alkylation); Granacher (arylpropanoic acid); Freeman (Li DBB ketone alkyl);
Fujiwara (ketone condens Yb); Gattermann–Koch (arom carbonylation); Gilman–Speeter
(b-lactams synth); Gilman–van Ess (ketone synthesis); Girard (RNHNH2 reagent); Ghosez
(cyclobutanone synth); Grignard (RMgX þ C¼O); Hayashi (ArCOOH rearr); Hiyama–Heath-
cock (Cr allylation); Hoffman–Yamamoto (B allylation); Hoppe (asym carbamate allylation);
Horner–Wasworth–Emmons (via phosphonates); Ivanov (Grignard from RCH2COOH);
Kagan–Molander (Sm); Lapworth (benzoin synth); Kaiser–Johnson–Middleton (via dinitriles);
Knoevenagel (cinnamic acid synth); List (asymMannich); Luche (Zn allylation); Mander (car-
bomethoxylation); Nagata (cyanohydrin synth Al); Ohira–Bestmann (acetylenes from diazo-
phosphonate); Oppolzer (Zn asym); Passerini (with isocyanide); Pedersen (Nb with imines);
Prelog–Stoll (acyloin); Reetz (selective alkyl Ti); Reformatzky–Blaise (Zn and halo ester);
Seebach–Beck (TADDOL cat Grignard, aldol); Seebach–Corey (rx w dithiane); Seyferth (acyl
lithium); Seyferth–Colvin–Gilbert (via diazo); Speckamp ((acyliminium); Stetter (1,4-add);
An Overview of Synthesis Related Name Reactions xxi
Stiles–Sisti (RMg formylation); Stork (via enamine); Szarvasy–Schoepf (carbomethoxylation);
Takai (olefination Zn); Taylor–Ireland (alcohol olefination P); van Leusen (cyanation);
Weinreb (via amide Li); Widequist (halomalononitrile); Wissner (hydroxyketone synth);
Wittig (olefination P).
(ene-diynes); Blomquist (macrocycle); Berchtold (enamine homologation); Bradsher (anthra-
cene synth); Diels–Alder; Danishefsky (hetero Diels–Alder); Dieckmann (ester–ester cond);
Conia (C¼O olefin ene rx); Cope (diene rearr); Danheiser (vinyl Si Ti); Doetz (hydroquinone);
Elbs (polynuclear); Felkin (Mg ene); Franchimond (cyclobutanone synth); Grubbs (Ru olefin
metathesis); Hafner (azulene synth); Kaiser–Johnson (dinitrile); Kennedy (Re O-cycliz);
Mascarelli (fluorenone synth); Parham (RLi); Pauson–Khand (cyclopentenone via CO);
Prelog–Stoll (acyloin); Pschorr (diazonium þ arom); Robinson (Michael–aldol annulation);
Stork (radical); Stork (reductive w Li–NH3); Story (macrocycle synth); Toste (alkyne Au
cat); Wender (homo Diels–Alder); Zinke–Ziegler (calixarene synth); Scholl (polyaromatic);
Ziegler (macrocycle).
Cycloadditions: Alder–Rickert (D–A); Bailey (criss-cross C¼O); Bergman (cycloaromati-
zation); Bestmann (w P-ylides); Boeckelheide (heterocycl ring expansion); Boger (cyclopen-
tane synth); Boger–Carboni (hetero D–A); Bradsher (isoquinolinium D–A); Brandi–Guarna
(nitrile oxide, rearr); Fleming–Mah (anthracene synth 2 þ 2); Fokin (alkyne þ azide click
rx, Cu cat); Danishefsky (hetero D–A); DeMayo (2 þ 2 photo); Diels–Alder; Diels–Alder
(asym); Finegan (azide-nitrile); Fleming–Mah (benzyne 2þ 2); Ghosez (cyclobutanone synth);
Hassner–Ghera–Little (methylenecyclopentane synth); Hetero Diels–Alder; Huisgen (dipolar);
Kinugasa (nitrile oxide); Larock (vinylcyclopropane annulation); Myers (cycloarom); Paterno–
Buechi (photo 2þ 2); Pfaltz–Evans (asym D–A); Staudinger (ketene); Trost (methylenecyclo-
pentane synth; Wender (homologous D–A).
Cyclopropane Synthesis: Bertrand–Stephan (via carbenes); Boger (cyclopentane synth);
Brandi–Guarna (spirocyclopropane rearr); Ciamician–Dennstedt (CCl2 addition); Cloke–
Wilson (cyclopropyl ketone rearr); Doering–La Flamme (from allenes); Fischer (via carbene);
Freund–Gustavson (from C–Br); Hassner–Ghera–Little (MIRC); Kagan–Molander (via Sm);
Kulinkovich (cyclopropanol synth); Mousseron–Fraisse–McCoy (from halo ester); Nerdel
from enol ether); Pfaltz–Evans (bisoxazolines); Pfau–Plattner (via diazo); Seyferth–Gilbert
(via diazophosphonate); Seyferth (via dihalocarbene); Simmons–Smith (Zn, Sm carbene);
Skattebol (from allenes); Srebnik–Quntar (cycloprop phosphonate); Toste (Au catalyzed);
Wender (homologous D–A); Widequist (from halomalononitrile).
Cyclopropane rxs: Boger (thermal cyclopentene synth); Brandi–Guarna (spirocyclopro-
pane rearr); Ciamician–Dennstedt (dichlorocyclopropane); Cloke–Wilson (cyclopropyl ketone
rearr); Doering–La Flamme (allenes from dihalocyclopropanes); Feldman (vinylcyclopropane
rearr); Fischer (carbene); Favorski (haloketone rearr); Nerdel (ether homologation); Haller–
Bauer (ketone cleavage); Kulinkovich (cyclopropanol synth); Skattebol (vinyl cyclopropane
rearr); Simmons–Smith (Zn carbenoid); Wender (vinylcyclopropane D–A).
Epoxides: Adler (spiro from phenols); Corey (epox from C¼O); Curci–Murray (via dioxir-
anes); Darzens (Zn from haloesters); Hassner–Rubottom (ketone hydroxylation via epoxides);
Jacobsen (asym); Julia–Colonna (asym); Sharpless (asym); Lautens (vinylepoxide rx); Martin
(dehydration); Payne (rearrangement); Sharpless (asymmetric synth).
Fluorine Compounds:Burton (nucleophilic CF3); Comins (triflating reag); Gingras (OTf to
F via SnF); Johnson (arom alkynylation); Knunyants (F-alkyl); Mosher (chirality determina-
tion); Rozen (hypofluoride rxs); Ruppert (nucleophilic perfluoroalkylation); Schiemann
(aromatic fluorination); Seyferth (difluorocarbene rx); Smith–Middleton–Rozen (C¼O fluori-
nation); Swarts (Cl to F); Togni (electrophilic CF3); Vorbruggen (OH to F).
xxii An Overview of Synthesis Related Name Reactions
Free Radical Reactions:Barton (deamination); Barton (nitrite photo rx); Barton (decarbox-
ylation); Barton–McCombie (via xanthate); Bergman (cycloarom); Cella–Piancatelli
(IBX-TEMPO oxid); Chatgilaloglu (Si dehalogenation); Dowd (ring expansion); Feldman
(vinylcyclopentane synth); Giese (C¼C additions); Jeger (THF synth); Keck (allylation);
Kharash–Sosnovsky (oxidation, Cu); Kuivila–Beckwith (dehalogenation); Minisci (arom sub-
stitution); Myers–Saito (cycloarom); Nugent–Rajanbabu (from epoxides Ti); Stork (rad cycl);
Stork (red cycl); Suarez (hypervalent iodine rx); Treibs (allylic oxid); Wohl–Ziegler (bromina-
tion); Zard (radical aminomethylation).
Halogen Except F: Appel (displacement via P); Barleunga (pyridine iodonium); Barton
(decarboxylation); Blanc–Quellet (haloalkylation); Boord (Br enol ether); Brown (I, functional
group); Cella–Piancatelli (IBX OH-oxid); Chatgilialoglu (Si dehalogenation); Cristol–Firth
(halodecarboxyl Hg); Feist–Benary (Br furan synth); Finkelstein–Gryszkiewicz (displacement
Br, Cl, F); Freund–Gustavson (Br, Cl cylopropane synth); Hassner (iodine azide); Hassner–
Rubuttom (a-haloketones synth); Hell–Volhardt–Zelinski (a-halo acids); Hunsdiecker (halode- carboxylation); Julia–Bruylants (homoallyl synth); Keinan (red I); Kochi (halodecarboxyla-
tion); Khun–Winterstein (alkene synth I); Kuivila–Beckwith (Bu3SnH dehalogenation);
Lemieux–Johnson (IO4, diol oxid); Mukaiyama (lactonization halopyridinium); Nicolaou
(IBX OH-oxid); Oshiro (Br red); Suarez (ROI); Stieglitz (chloroamine rearr); Varvoglis–
Moriaty (hypervalent I); Vohl–Ziegler (bromination via NBS).
N-Heterocycle Synthesis 5-Rings: Asinger (thiazoline); Baeyer (oxindole); Baeyer–
Drewson (indoxyl); Bailey (diazabicyclooctanes); Bamberger (imidazole); Bischler–Mohlau
(indole); Boulton–Katritzky (oxadiazole rearr); Bredereck (imidazole); Bucherer–Bergs
(hydantoin); Cadogan–Cameron–Wood (cycl via NO2); Chichibabin (indolizidine);
Clauson–Kaas (pyrrole); Cornforth (oxazole); Davidson (oxazole); Dimroth (triazole);
Dondoni (thiazole); Erlenmeyer–Plochl (AA via oxazolone); Finegan (tetrazole); Fischer–
Borsche–Drexel (indole); Fischer (oxazole synth); Fokin (triazole, click rx): Gabriel–Heine
(imidazoline); Gassman (oxindole); Gewald (aminothiophene, pyrrole); Groebke–Blackburn–
Bienyame (imidazole); Hinsberg (thiophene); Hantsch (thiazole); Hassner (C¼C to tetrazole);
Hassner–Ghera–Little (pyrrolines); Herz (benzothiazole); Hinsberg–Stolle (indole); Hofmann–
Loeffler–Freytag (pyrrolidine); Huisgen (oxadiazole); Huisgen (zwitterions); Johnson (alkyne
to indole); Japp (oxazole); Kawase (oxazole rearr); Kennedy (THF); Knorr (pyrazole); Kohler
(isoxazoline); Larock (indole); Leimgruber–Batcho (indole); List-MacMillan (imidazolium
C¼C hydrogenation); MacDonald (porphyrin); Madelund (indole); Meyers (asym oxazoline
rxs); Neber–Bosset (oxindole); Nenitzescu (indole); Overman (pyrrolidine); Paal–Knorr (pyr-
role); Padwa (pyrroline); von Pechman (pyrazoline); Pfaltz–Evans (bisoxazolines asym rxs);
Pilloty–Robinson (indole); Reissert (indole); Robinson–Fould (indole); Robinson–Gabriel
(oxazole); Rothemund–Lindsey (porphyrin); Sandmeyer (isatin); Schoellkopf–Barton–Zard
(pyrrole); Scholtz (indolizine); Schweizer (pyrazole); Shibasaki (indole); Shibasaki (Ti
N-insertion); Staab (C¼O diimidazole); Traube (purine); Van Leusen (isonitrile); Wallach
(imidazole); Watanabe (indole, Ru); Weidenhagen (imidazole); Wilkes–Armstrong (ionic liq,
asym imidazolium); Wilkes–Armstrong (ionic liq, imidazolium); Yonemitsu (3-component in-
dole synth); Zav’yalov (pyrrole).
Heterocycle Synthesis Other 5-Rings: Buchwald (Zr, heterocycl, also N); Feist–Benary
(furan); Garst–Spencer (furan); Hinsberg (thiophene); Jeger (THF synth); McCormack–
Kuchtin–Ramirez (phosphole); Mascarelli (benzofuran); Nikl (benzofuran); Perkin (benzofuran);
Rapp–Stoermer (benzofuran); Vollhardt–Erdmann (thiophene); Jeger (tetrahydrofuran).
N-Heterocycle Synthesis 6-Rings: Baeyer (pyridine); Bamberger (benzotriazine);
Bernthsen (acridine); Biginelli (pyrimidone); Bischler (benzotriazine); Bischler–Napieralski
(isoquinoline); Boeckelheide (pyridine); Boger–Carboni–Lindsey (hetero D–A); Blicke–
An Overview of Synthesis Related Name Reactions xxiii
Pachter (pteridine);Bradsher (isoquinoline viaD–A);Brandi–Guarna (pyridones fromspirocyclo-
propane); Burgess (oxazine); Cadogan–Cameron–Wood (cycl via NO2); Camps (quinolinone
synth); Chichibabin (arylpyridine); Combes (quinoline); Corey–Nicolaou–Gerlach (lactonization
w pyridinethiol); Doebner–Miller (quinoline); Emmert (pyridine alkyl); Gould–Jacobs (quino-
lone); Grubbs (via Rumetathesis); Ferrario–Akermann (thiocyclization); Friedlander (quinoline);
Gabriel–Colman (isoquinolines); Gastaldi (pyrazine); Guaresky–Thorpe (pyridine); Haddadin–
Issidorides (quinoxaline); Hammick (pyridine alkylation); Hanaoka–Wrobel (quinolizidines);
Hantsch (dihydropyridine); Hilbert–Johnson (nucleoside); Hofmann–Loeffler–Freytag (piperi-
dine); Kaiser–Johnson–Middleton (pyridine etc); Koenig (benzoxazine); Knorr (quinoline);
Ladenburg (pyridine benzylation); Lehmsted–Tanasescu (acridone); Leuckart–Pictet–Hubert
(phenanthridine); List-MacMillan (dihydropyridine C¼C hydrogenation); Mukaiyama (lactoni-
zation w halopyridinium); Meerwein (O-alkylation); Mukaiyama (lactonization w halopyridi-
nium); Mundi (N-acyllactam rearr); Niementowski (quinazolone); Pfitzinger (quinoline);
Pictet–Hubert–Gams (isoquinoline); Pomeranz–Fritsch–Schlitter–Muller (isoquinoline);
Remfry–Hull (pyrimidine); Reisssert (cyano-isoquinolines); von Richter–Widman–Stoermer
(cinnoline); Robinson–Fould (quinoline); Simchen (rearr to isoquinoline); Skraup (quinoline);
Speckamp (N-rings); Stieglitz (haloamine rearr); Timmis (pteridine); Traube (purine);
Ullmann–Fedvadjan (acridine); Ullmann–Horner (phenazine); Ullmann–La Torre (acridine);
von Richter–Widman–Stoermer (cinnoline);Westphal (quinolizidine); Yamaguchi (lactonization
w DMAP Cl3PhCOCl); Yamazaki (pyrimidine); Yamazaki–Clausen (guanine).
Heterocycle Synthesis of Other 6-Rings: Achmatowicz (pyranone from furan); Auwers
(flavone); Baker–Venkataraman (flavones); Balaban–Nenitzescu–Prail (pyrylium salts);
Ferrario–Ackermann (phenothiazine); Hetero Diels–Alder (pyrans); Kabe (chromanone);
Menzer (benzopyran); Mueller (thiochromone); von Pechmann (coumarin); Robinson–
Allan–Kostanecki (chromone); von Pechman–Duisberg (coumarin).
Heterocycles (Miscellaneous): Abramov (oxazaphosphole); Allen–Millar–Trippett (phos-
phinine); Alper (lactams); Blum (aziridine); Breckport (b-lactam); Davies (b-lactam); Davis
(oxaziridine reag);DeKimpe (aziridine); Gabriel–Heine (aziridine);Gilman–Speeter (b-lactams);
Graham (diaziridine); Hassner (azirine); Hesse–Schmid (Zip polyamines); Kaiser–Johnson–
Middleton (via dinitriles); Hoch–Campbell (aziridine); Kinugasa (b-lactam); Lehn (N,O cryp-
tand); McCormick–Kutchin–Ramirez (phosphole); Mukaiyama (lactone); Parham (cycl);
Paterno–Buechi (oxetane); Pedersen (crown ethers); Scheiner (aziridine); Schmidt (azepine by
rearr); Schmitz (diaziridine); Speckamp (acyliminium); Staudinger–Pfenninger (thiiranes);
Wasserman–Bormann (macrocycl lactam); Wenker (aziridine).
Hydrogenation Catalytic: Bertrand–Stephan (metal free); Crabtree (Ir selective); Eckert
(Co, Pd); Kagan–Horner–Knowles (Rh); Lindlar (Pd); List-MacMillan (metal free); Noyori
(homogen hydrogenation Ru BINAP); Pearlman (Pd hydrogenolysis); Rosenmund (aldeh from
acid chloride Pd).
(aminophosphonate); Mannich (b-aminoketone synth); Morita–Baylis–Hillman (hydroxy al-
kene syn); Mueller (thiochromone synth); Passerini (acyloxy amides); Pauson–Khand (cyclo-
pentenone); Petasis (amine synth B); Rauhut–Currier (Michael–Michael); Strecker (AA synth);
Ugi (diamides, AA); Yonemitsu (3-component).
Olefin Formation (via C + C Except Pd C–C Coupling): Barton–Kellogg (via thioke-
tones); Bestmann (via phosphocumulene); Boord (enol synth); Corey–Chan (alkylation of al-
kynes); Eschenmoser (methylenation); Eschenmoser–Stoltz (via aziridinehydrazones); Gold
xxiv An Overview of Synthesis Related Name Reactions
(methylenation); Grob–Eschenmoser (fragmentation); Grieco (via Se from ROH); Grubbs (di-
ene metathesis Ru); Hiyama (aminoacrylate); Horner–Wadsworth–Emmons (via phospho-
nates); Julia–Lythgoe (via sulfones); Julia–Kocienski (via sulfones); Katritzky–Li (via
benzotriazoles); Knoevenagel (malonateþ PhCH¼O); Kocienski–Fugisawa (Cu substitution);
Ramberg–Backlund–Paquette (SO2 elimination); Reich–Krief (via Se from ROH); Robinson
(cyclohexenone synth); Ruppe (from acetylenic alc); Saegusa (enone synth Pd); Shapiro (from
tosylhydrazones); Siegrist (stilbene synth); Skattebol (from dihalocyclopropanes); Takai (from
C¼O Zn); Tschugaef (via xanthates); Wharton (from hydrazinone); Petasis (via Ti); Peterson
(from silane þ C¼O); Still–Gennari (Z via trifluoroethyl phosphonates); Stork–Zhao
(Z-iodoalkene synth); Takai–Nysted (from CH2X2 Zn–Ti); Taylor–Ireland (alc þ P-ylide);
Tebbe–Grubbs (w Ti–Al); Wittig (via P-ylides).
Olefin Formation (via Elimination): Bamford–Stevens (from tosylhydrazone); Barton–
McCombie (from dixanthate); Burgess (–H2O); Chugaev (via xanthates); Clive–Reich–
Sharpless (from selenoxide); Concellon (Z-olefin synth); Cope–Mamloc–Wolfenstein (from
amine oxides); Corey–Winter–Eastwood (via dioxalanes); Crabee (allene synth); Doering–
La Flamme (allene synth); Garegg–Samuelson (from diols); Grob–Eschenmoser (fragmenta-
tion); Grieco (from ROH via Se); Grubbs (metathesis Ru); Hofmann (from ammonium salts);
Julia–Bruylants (cycloprop carbinol rearr); Julia–Lythgoe (via sulfones); Julia–Kocienski (via
sulfones); Knoevenagel (malonateþ PhCH¼O); Khun–Winterstein (from diol); Martin sulfur-
ane (from ROH); Mattox–Kendall (dehydrohalogenation); Migita–Sano (quinodimethane
synth); Peterson (from Si, OH); Ramberg–Backlund–Paquette (SO2 elimination OH); Robinson
(cyclohexenone synth); Ruppe (from acetylenic alc); Saegusa (enone from ketone Pd); Shapiro
(from tosylhydrazones); Siegrist (stilbene synth); Skattebol (from dihalocyclopropanes);
Tschugaef (via xanthates); Wharton (via hydrazone); Whiting (diene synth).
Oxidations: Achmatowicz (pyranone synth from furans); Adler (of phenols); Baeyer–
Villiger (ketone to ester); Baudisch (nitrosophenol synth); Barbier–Wieland (ester chain deg-
radation); Barluenga (pyridine iodonium); Boyland–Sims (aminophenol synth); Cannizzaro
(oxid-red); Cella–Piancatelli (of alc w IBX-TEMPO); Cooper–Finkbeiner (C¼C oxidation
via Mg); Corey (ketone epoxidation); Corey (of alc by Cr PCC); Corey–Kim (of alc
w Me2S-NBS); Criegee (diol w Pb(OAc)4); Criegee (hydroperoxide rearr); Curci–Murray
(w dioxirane); Davis (oxaziridine reag); Dakin (arom C¼O to phenol); Delepine (aldeh oxid
Ag); Dess–Martin (of alc by periodinane); Djerassi–Rylander (of ethers, amides Ru); Doering
(of alc w pyr SO3); Doyle (Rh allyl oxid); Elbs (of aromatics w persulfate); Ehrlich–Sachs
(aromMe to CH¼O); Etard (Me to CH¼O); Guilemonat–Sharpless (allylic); Harries (via ozon-
ide); Hass–Bender (C–Br to C¼O); Hooker (quinine synth); Jacobsen (asym epox); Jones (of
alc w CrO3-H þ); Julia–Colonna (asym epoxide synth); Kagan–Modena (sulfoxide synth);
Kakis (oxid aryl rearr); Kametani (amine to nitrile); Kharash–Sosnovsky (allylic Cu); Konaka
(Ni peroxide reag); Kornblum (ald from alkyl halide); Lemieux–Johnson (C¼C to diol); Ley–
Griffith (of alc by perruthenate); Lieben (of Me–ketone w NaOCl); Miescher (chain degrada-
tion); Milas (diol synth); Mukaiyama–Ueno (of diols, Sn); Nicolaou (OH-oxid by IBX); Oppe-
nauer (of alc by Al(OiPr)3); Pfitzner–Moffat (of alc by DMSO-DCC); Pinnick (aldeh to
RCOOH w NaClO2); Riley (w SeO2); Pfitzner–Moffat (of alc w DMSO); Sarett (of alc
w CrO3-pyr); Schenck (allylic); Sommelet (aldeh from alkyl halide); Spengler–Pfannenstiel
(sugar); Story (macrocycle synth from ketones); Swern (oxid of alc by DMSO-(COCl)2);
Tamao–Fleming (RSi to ROH); Taylor–Ireland (alc olefination); Teuber (quinone synth); Tra-
hanovsky (of ethers CAN); Treibs (allylic); Uemura–Doyle (allylic Rh); Varvoglis–Moriarty
(w DIB); Uemura–Doyle (allylic Rh); Vedejs (ketone hydroxylation Mo); Wacker–Tsuji
(olefin Pd–O2); Weerman (amide degradation); Wilkinson (w O2 Rh).
An Overview of Synthesis Related Name Reactions xxv
P, As Compounds: Abramov (OH-phosphonate); Allen–Millar–Trippett (phosphonium
rearr); Appel (displacement via P); Arbuzov–Michaelis (phosphonate synth); Atherton–Todd
(phosphoramidate synth); Bart–Scheller (arsenylation); Bechamp (arsenylation); Bestmann
(P-ylides); Clay–Kinnear (P–Cl synth); Erlenmeyer–Plochl (AA P); Kabatchnik–Fields (ami-
nophosphonate); Mann (ether dealkylation by phosphide); McCormick–Kutchin–Ramirez
(phosphole); Michaelis–Nylen (phosphonate); Ohira–Bestmann (synth via P-ylide); Oleksys-
zyn (amino phosphonic acid); Perkow (vinyl phosphonate); Pudovik (OH-phosphonate);
Rauhut (Michael–Michael); Rosenmund (arsenylation of ArBr); Srebnik–Quntar (cycloprop
phosphonate); Taylor–Ireland (alc olefination w P-ylide); van Boom (phosphorylation);
Schwesinger (N, P base); Seyferth–Gilbert (diazophosphonate); Wilkes–Rogers (P ionic
liq); Wissner (OH-ketone synth).
DeMayo (2þ 2 cycloadd of alkenes); Moore–Danheiser (alkenylcylobutenone rearr); Paterno–
Buechi (2 þ 2 cycloadd of C¼O); Suarez (of hypoiodide); Wolfram–Schoernig–Hansdorf
(carboxymethylation).
Rearrangements: Achmatowicz (furan to pyranone rear); Acyloin (OSi rearr); Allen–
Millar–Trippett (phosphonium); Amadori (aminosugars); Baker–Venkataraman (ketoester to
flavones); Arndt–Eistert (diazoketone to ketene); Auwers (dienone to phenol); Black (enol car-
bonate rearr); Boulton–Katritzky (oxadiazole); Brandi–Guarna (pyridones from spirocyclopro-
pane); Brook (Si–ketone rearr); Bradsher (isoquinoline via cations); Brandi–Guarna (nitrile
oxide cycloadd); Cargill (cyclobutenyl ketone rearr); Carroll (allyl ketoester rearr); Chan (acy-
loxyacetate rearr); Chapman (O to N rearr); Cloke–Wilson (cyclopropyl ketone rearr); Colvin
(alkynes via carbenes); Cornforth (oxazole rearr); Criegee (hydroperoxide rearr); Curtius
(amine from acyl azide); Demjanov (via diazonium); Dimroth (N-R rearr); Ferrier (carboh
rearr); Fischer (indole synth); Fittig (pinacol); Fries (phenol ester); Fritsch–Buttenberg (alkyne
synth); Gabriel–Colman (phthalimide rearr); Grovenstein–Zimmermann (carbanion rearr);
Gabriel–Heine (acylaziridine); Garst–Spencer (vinylepoxide); Hayashi (o-benzoylbenzoic); Hofmann–Martius (of anilines); Hooker (quinone rearr); Huisgen (tetrazole); Johnson (alkyne
synth); Johnson–Claisen (allyl orthoacetate rearr); Julia–Bruylants (cycloprop carbinol);
Kinugasa (asym cycloadd); Kakis (oxid aryl rearr); Kawase (acyl rearr); Koch–Haaf (carbox-
ylation); Kreszge (S amination); Liebig (benzylic acid synth); Lossen (hydroxamic acid to
amine); Meinwald (epox rearr); Meyer–Schuster (propargyl); Morin (S¼O rearr); Moore–
Danheiser (alkenylcylobutenone rearr); Mundi (N-acyllactam); Overman (O to N allyl);
Pummerer (S¼O); Schmidt (azide rearr); Simchen (N-heterocycl); Sommelet (ammonium);
Stephens (ammonium); Steglitz (via nitrene); van Leusen (isonitrile þ C¼O); Wagner–
Meerwein (carbocation); Wallach (azoxybenzene); Wessely–Moser (hydroxyxanthone);
Westphalen–Letree (carbocation); Willgerodt (thioamide rearr); Zinin (benzidine rearr).
Rearrangements Sigmatropic: Alder (ene rx); Carroll ([3,3] allyl acetoacetates); Claisen
([3,3] allyl enol ethers, also thia, aza); Conia (1,5-ene cyclization); Cope (3,3 1,5-dienes);
Eschenmoser–Meerwein (3,3 allylic N,O-ketene acetals); Felkin (Mg-ene cyclization);
Frankel–Shibasaki (1,5-H); Fries (phenol esters); Guilemonat–Sharpless (allylic oxid); Ireland
(3,3 silyl enolate of allyl esters); Johnson (3,3 allyl orthoacetates); Kirmse–Doyle (allyl sul-
fide); Kreszge (S amination); Meisenheimer (N-oxide); Mislow–Braverman–Evans (2,3 allyl-
sulfoxide); Newman–Kwart (thiophenol); Nokami (allyl alkylation); Overman (3,3 allyl O to N
rearr); Overman (3,3þ aldol aza-Cope–Mannich); Oxy-Cope (3,3); Reformatzky–Claisen (3,3
allyl a-bromoesters via Zn); Wittig (2,3 allyl ether).
Reductions (Excluding Pd Catalyzed Hydrogenation): Barton–McCombie (deoxygen-
ation); Birch (arom w Li–NH3); Bischler (nitrophenylhydrazine red); Bertrand–Stephan
xxvi An Overview of Synthesis Related Name Reactions
(hydrogenation); Borch (ketone to amine); Bouveault–Blanc (w Na–ROH); Bouveault–Loquin
(Ni N¼O red); Brown (asym ketone red); Brown (C¼O red agents); Caglioti (C¼O red);
Cannizzaro (oxidation-reduction); Chatgilialoglu (w silanes); Clemmensen (Zn, C¼O red); Co-
rey (asymB); Corey–Chan (propargyl LAH); Emmert (pyridine–ketone cond); Evans (1,3-anti- diol synth); Fujiwara (w Yb, La); Hassner (azirine to aziridine); Henbest (w Ir); Keinan
(w diiodosilane); Kursanov–Parnes (w SiH); Leuckart (ketone to amine); List-MacMillan
(C¼C hydrogenation w dihydropyridine); Luche (C¼O red Ce); McFadyen–Stevens (RCOOEt
! RCH¼O); Meerwein–Ponndorf (w La(OiPr)3); Midland (asymmetric C¼O red); Minami
(aldehyde to alc); Moore–Danheiser (alkenylcylobutenone rearr); Oshiro (C¼CBr by phos-
phite); Reissert (ald synth); Rosenmund (Pd, aldeh from R(C¼O)–Cl); Staudinger (azide
red); Stephen (Sn RCN to RCH¼O); Stryker (Cu conjugate red); Suzuki (RCN to amine);
Tischenko–Claisen (OH-ketone red); Traube (w Cr(II)); Wenzel–Imamoto (La–Ni selective
hydrogenation); Wilkinson (Rh cat); Wolff–Kishner (C¼O to CH2 w hydrazine).
S, Se, Si, Sn, Bi Compounds: Acyloin rearr (enolsilane); Barton (Bi phenylation); Barton
(decarboxylation S); Brook (Si–C¼O rearr); Bucherer–Bergs (thiohydantoin rx); Chan–
Brassard (Si aldol); Chatgilialoglu (SiH red agent); Clive–Reich–Sharpless (C¼C from selen-
oxide); Commins (enol triflate synth); Corey–Nicolaou–Gerlach (pyr disulfide for lactoniza-
tion); Danheiser (C¼C–Si annulation); David–Thieffry (Bi O-phenylation); Davis–Ellman
(sulfinimines); Eschenmoser (C–S–C contraction); Flood (Si–Cl synth); Ferrario–Akermann
(S insertion); Freudenberg–Schoenberg (thiophenol synth); Fukuyama (thioester coupl); Giese
(Sn, rad); Gingras (ArSnF reag); Grieco (Se olefination); Guilemonat–Sharpless (allylic oxid
Se); Hassner–Rubbottom (C¼O a-functionalization via enolsilane); Hayashi–Uozumi (hydro-
silation); Hiyama–DeShong–Denmark (C–C coupling via Si Pd); Ireland (Si allyl ester rearr);
Kagan–Modena (S oxid); Kahne (sugars via S¼O); Keinan (SiH red); Kirmse–Doyle (allylsul-
fonium rearr); Koser (tosylation); Kreszge (S amination); Kuivila–Beckwith (dehalogen
w Bu3SnH); Kursanov–Parnes (SiH reag); Liebeskind (S-ester coupl); Lawesson (C¼S from
C¼O); Leuckart (thiophenol synth); Morin (S¼O rearr); Mueller (thiochromone synth);
Mukaiyama (aldol via Si enol ether); Mukaiyama–Ueno (diol oxid, Sn); Newman–Kwart
(thiophenol from phenol); Nishimura–Cristescu (Si nucleoside synth); Oppolzer (chiral sultam);
Pinhey (B arylation); Pummerer (S¼O rearr); Seebach–Corey (S dithiane rxs); Staudinger–
Pfenninger (thiiranedioxide synth); Stephen (CN red, SnCl2); Stille (Sn carbonylation);
Stille–Milstein (Sn–Pd coupling); Takei–Casiraghi (siloxyheterocycle þ C¼O); Tamao–
Fleming (R-Si to ROH); Vorbrueggen (nucleoside synth via Si); Willgerodt (thioamide rearr);
Yamamoto (aldol via super Si); Zard (xanthate rad rx); Zeisel–Prey (Si ether cleav).
Sugars-Carbohydrates, Nucleosides: Amadori (aminosugars); Baer–Fischer (amino
sugar); Ferrier (chiral cyclohexanone from sugar); Ferrier (carboh rearr); Hilbert–Johnson
(nucleoside synth); Kahne (sugars via S¼O); Kiliani–Fischer (sugar homolog synth);
Koenigs–Knorr (glucosidation synth); Nishimura–Cristescu (nucleoside synth); Purdie (sugar
methylation); Spengler–Pfannenstiel (sugar degradation); Suarez (hypervalent iodine and
sugar); Vasella–Bernet (cylopentane synth from sugars); Vorbrueggen (nucleoside synth);
Wohl–Weygand (sugar degradation).
Thermal Reactions: Bechamp (arsonylation); Boger (thermal cyclopentene synth);
Brandi–Guarna (pyridones from spirocyclopropane); Bredereck (imidazole syn); Chapman
(O to N rearr); Chugaev (xanthate elimin); Claisen (allyl vinyl ether rearr); Conia (cycl); Cope
(diene rearr); Dakin–West (decarboxylation); Diels–Alder; Elbs (polynuclear synth); Finegan
(azide-nitrile cycloadd); Freudenberg–Schoenberg (thiophenol synth); Gould–Jacobs (quino-
lone); Hofmann (elim of ammonium salt); Krapcho (decarbethoxylation); Hunsdiecker (halo-
decarboxyl); Roelen (Co, hydroformylation).
An Overview of Synthesis Related Name Reactions xxvii
Overview - Pd Catalyzed C–C Coupling Name Reactions
Most Pd catalyzed reactions appear to involve the following catalytic cycle
Pd(0)
L
L
L
L
isomerization
Some examples of Pd catalyzed coupling, for details see respective name reactions
Beller: ArCH=O + RCO–NH2 + CO RCO–NH–CH(Ar)–CO2H PdCl2
Fukuyama: RZnI + R¢(CO)–S–Et R–(C=O)–R¢ PdCl2
Fujiwara: C=C + CO (or CO2) + (O) C=C–COOH Pd(OAc)2
Heck–Fujiwara–Mizoroki: R–C=CAr–C=C X : Br, I, N2 +
Br
OHC
+ O
Pd(II) cat
130 °C
Hiyama–DeShong–Denmark: RX + Ar–Si(OR¢)3 R–Ar X : Br, I, OTf
Si(OMe)3
+
Kumada–Corriu–Tamao: RX + R¢MgX R–R¢ Ni or Pd catalysis
Cl
MeO
n-Bu
MeO
Liebeskind: Ar–CO–S–Et + Ar¢-B(OH)2 Ar–CO–Ar¢ Pd or Cu
Negishi: RX + R¢C=C–ZnX R–C=C–R¢ Pd or Ni catalyzed
Bu3Sn ZnCl
O
O +
Stille CO: RX + C=CSnR¢3 + CO R–CO–C=C
OTf
SnBu3
R
Cl
CO2Et
Suzuki–Miyaura: RX + R¢BY2 R–R¢ Pd (or Ni)
+ B(OR) I
2 Ph3As
Tsuji–Trost allylation: (soft carbanion and allyl ester or carbonate)
O
O
NaOH
O
O
O
Yamamoto allylation: R–CH=NR¢ + C=C–C-SiR¢3 (or Sn) R (C*–NR¢)–C–C=C
xxx Overview - Pd Catalyzed C–C Coupling Name Reactions
List of Abbreviations
9-BBD 9-Borabicyclo[3.3.2]decane
9-BBN 9-Borabicyclo[3.3.1]nonane
HTIB Hydroxy(tosyloxy)iodobenzene
IBA Isobutyraldehyde
MOM Methoxymethyl
PTSA (TsOH) p-Toluenesulfonic acid
TEA Triethylamine
TTMSS Tris(trimethylsilyl)silane
ABIKO–MASAMUNE Asymmetric Aldol Reaction
Asymmetric aldol reaction between propionate esters e.g. 1 and aldehydes 2 using (þ) or () nor-
epinephrine (or norephedrine) as a chiral auxiliary; proceeds via ester boron enolates 4. Formation
ofpreferentially syn3 oranti2 productsdependson thebulkiness of alkyl in the dialkylboron triflate, as well as on the chiral auxiliary, the tert amine and temp (lower temp favors kinetic anti product); the large dicyclohexylboron triflate 4 leads predominantly to anti products 3 via E-boron ester
enolates, while dibutylboron triflate and DIPEA give more syn aldols.10 Double aldol reaction
of acetate esters is possible.6 Methoxyacetates give syn-glycolate derivatives with high
selectivity.8 Compare with Evans syn-aldol and Crimmins anti-aldol (via ketone enolates).
c-Hex2BOTf
4
5
2
2
anti Selective aldol (3).5 To a solution of norepinephrine ester (1R, 2S)-1 (4.80 g, 10 mmol) (R1¼ Bn,
R2 ¼ Mes) in CH2Cl2 (50 mL) in an oven-dried 500 mL flask under nitrogen was added via syringe
TEA (3.40 mL, 24 mmol). A solution of dicyclohexylboron triflate (1.0 M in hexane, 22 mL) was
added over 20 min at 78 C and stirring was continued for 30 min. IBA 2 (R ¼ iPr, 1.08 mL,
12 mmol) was then added dropwise and the mixture was stirred at78 C for 30 min and then brought
to r.t. (1 h). After quenching with a pH 7 buffer (40 mL), MeOH (200 mL) and 30% H2O2 (20 mL)
were added slowly. After stirring overnight at r.t. and usual workup and evaporation a solid was
obtained which was crystallized from hexane (150 mL) to give crude 3 (4.4 g). Removal of cyclohex-
anol from the mother liquor and chromatography provided an additional product (0.6 g). Crystalliza-
tion from EA–hexane (1:5) afforded 4.77 g (87%) of pure anti (þ)-3.
syn Aldol (3).5 As above, reaction of ester (1R, 2S)-1 (R1 ¼ Me, R2 ¼ octahydroanthracenyl(OHA),
0.4 mmol) with n-Bu2BOTf (0.8 mmol) and iPr2NEt afforded 3-syn (98%).
1 Brown HC Tet Lett 1992 33 3421
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10 Dai W-M Tetrahedron 2010 66 187
A
1
BINAP catalysts, leading to chiral hydroxyalkyl phosphonates 7.
N P
O PhCl
N P
O PhN
N P
Ph Ph ,
(S)-BINAPO
SiCl4
(S)-BINAPO
Diethyl hydroxybenzyl phosphonate (7).10 Phosphite 6 (1.50 mmol) was added to benzaldehyde 5
(1.0 mmol), iPr2NEt (1.50 mmol), and (S)-BINAPO (10 mol %) in DCM (4 mL) at 78 C. SiCl4 (0.75 M DCM solution, 2.0 mL) was added over 2 h with a syringe pump. Water (4 mL, deionized),
sat aq NaHCO3 (10 mL), and EA (10 mL) were added, the mixture was stirred for 1 h and filtered
through celite. Extraction with EA (3 10 mL), usual workup, and chromatography (silica gel
15 g, hexane:acetone 2:1 and 1:1) gave 7 (73%, 35% ee).
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10* Nakajima M Tetrahedron 2008 64 6415
2
Rearrangement of 2-hydroxyalkylfurans 1, 7 (or 2-aminoalkylfurans)4 to pyranose derivatives
4, 8 (or to 7-membered rings) by reaction with Br222MeOH,1 NBS,5 m-CPBA4 or TBHP-VO
(acac)2. 6 Also by anodic oxidation in MeOH.2
O O
O
Cl
TBSO TBSO
2-(Chloromethyl)-6-hydroxy-2H-pyran-3(6H)-one (8). 8 Freshly distilled acetyl chloride (5.64 g,
72.4 mmol)was added to a solution of 5 (7.96 g, 72.4 mmol) in CH3CN (20 mL) followed by ammonium
ceric nitrate (1.94 g, 3.56 mmol) in CH3CN (20 mL). After usual workup and flash chromatography over
silica gel (n-hexane/EA 3:1), product 6 was isolated as a yellow oil. To a solution of 6 (0.954 g,
6.624 mmol) in PhCH3 (20 mL) was added BH3SMe2 (2M in THF, 0.504 g, 6.624 mmol) in PhCH3
(10 mL), the mixture was stirred for 3 h at r.t. and then quenched with sat NH4Cl solution. After
usual workup and flash chromatography over silica gel (n-hexane/EA 3:1), pure 7 was isolated as
a pale yellow oil. Compound 7 (0.292 g, 2 mmol) was added to a solution ofm-CPBA (0.344 g, 2 mmol)
in CH2Cl2 (2 mL) at 0 C and the mixture was stirred fo