Imprimatur: Date, Signature tc2318ss.fm 11/15/18 · Efficient and Versatile Catalytic Systems for the N-Methylation of Primary Amines with Methanol Catalyzed by N-Heterocyclic Carbene

Imprimatur:

Date, Signaturetc2318ss.fm 11/15/18

Reviews and Full Papers in Chemical Synthesis

2018Vol. 50, No. 23

December ISyn thesis

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Synthesis 2018, 50, 4501–4524DOI: 10.1055/s-0037-1610284

U. GrošeljF. PožganB. ŠtefaneJ. Svete*University of Ljubljana, Slovenia

Syn thesis

as

Copper-Catalyzed Azomethine Imine–Alkyne Cycloadditions (CuAIAC)

R2

NN

R3 R1

R4

NN

R1

R2

R4

NN

R1

R4 R3

NN OR

4

R5

NN R1

R4

R3

Cu0, Cu+, or Cu2+

Review

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Synthesis 2018, 50, 4525–4538DOI: 10.1055/s-0037-1610288

E. R. El-SawyA. B. AbdelwahabG. Kirsch*Université de Lorraine, France

Utilization of 1H-Indole-3-carboxaldehyde as a Precursor for the Synthesis of Bioactive Indole Alkaloids

Review

4525

Imprimaturhttps://doi.org/10.1055/s-0037-1610288https://doi.org/10.1055/s-0037-1610284

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Synthesis 2018, 50, 4539–4554DOI: 10.1055/s-0037-1611014

E. Martinez de MarigortaJ. M. de los SantosA. M. Ochoa de RetanaJ. Vicario*F. Palacios* University of the Basque Coun-try, Spain

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Multicomponent Reactions in the Synthesis of γ-Lactams

N

O

N

O

A+B+C...N

O

S
hort Review
4539

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Synthesis 2018, 50, 4555–4568DOI: 10.1055/s-0037-1609943

A. CholewiakP. StepniakJ. Jurczak*Institute of Organic Chemistry, Polish Academy of Sciences, Poland

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Linear Neutral Receptors for Anions: Synthesis, Structure and Applications

S
hort Review
4555

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Synthesis 2018, 50, 4569–4576DOI: 10.1055/s-0037-1610305

T. Jin*L. Zhao*X. LiuL. SunJ.-F. LinZ.-B. Zheng*Chengdu University, P. R. of ChinaSichuan Institute for Food and Drug Control, P. R. of China

Recent Advances in the Total Synthesis of Clavaminols

C9H19

NH2

OH

C9H19

NHAc

OH

C9H19

NHAc

OH

HO

C9H19

NH2

OH

HO

R

NH2

OH

clavaminol BR = Z-non-5-enyl

R

NHAc

OH

clavaminol NR = i-C10H21

(–)-clavaminol A (+)-clavaminol C (+)-clavaminol H

deacetyl (+)-clavaminol H

Representative Clavaminol

Natural Products

S
hort Review
4569

https://doi.org/10.1055/s-0037-1610305https://doi.org/10.1055/s-0037-1609943https://doi.org/10.1055/s-0037-1611014

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Synthesis 2018, 50, 4577–4590DOI: 10.1055/s-0037-1610250

H. OkamotoK. TohT. MochizukiH. NakatsujiA. Sakakura*M. Hatano*K. Ishihara*Nagoya University, JapanOkayama University, Japan

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Chiral Pyrophosphoric Acid Catalysts for the para-Selective and Enantioselective Aza-Friedel–Crafts Reaction of Phenols

Feature

4577

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Synthesis 2018, 50, 4591–4605DOI: 10.1055/s-0037-1611065

W. SunP. TrincheraN. KurdiD. PalomasR. Crespo-OteroS. AfshinjavidF. JavidC. R. Jones*Queen Mary University of London, UK

as

Aryne-Mediated Arylation of Hantzsch Esters: Access to Highly Substituted Aryl-dihydropyridines, Aryl-tetrahydropyridines and Spiro[benzocyclobutene-1,1′-(3′,4′-dihydropyridines)]

C-2 arylation(if R = H)

C-3 arylation(if R ≠ H)

‘Hantzsch ester’

Regioselective C-2 or C-3aryne ene reaction Bioactive highly functionalizedN-heterocycles Access novel spirocyclicbenzocyclobutenes

N Me

Me

R

CO2EtEtO2C

ArN

EtO2C CO2Et

Me

H R

Me

H

HH

R1N

EtO2C CO2Et

MeMe

R

ArMe

N

CO2Et

Me

Me

R

EtO2C

Ar

arylation/spirocyclization

+

excess

R1

aryne

Feature

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Synthesis 2018, 50, 4606–4610DOI: 10.1055/s-0037-1610659

D. BaidilovM. MakarovaL. RycekT. Hudlicky*Brock University, Canada

Preparation of Rearranged Allylic Isocyanates from the Reaction of Allylic Alcohols with 1-Cyano-4-dimethylaminopyridinium Bromide

OHR2

R3

R1 BrCN, DMAP

CH2Cl2, 0 °C to rtone synthetic operation

R1

R3

N

R2

CO

9 examplesup to 74% yield

PSP

4606


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Synthesis 2018, 50, 4611–4616DOI: 10.1055/s-0037-1609554

T.-S. Jiang*Q. ZhangG. LiX. ChengY. Cai*Anhui Agricultural University, P. R. of China

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DDQ-Mediated Oxidation of Allylarenes: Expedient Access to Cinnamaldehyde-Containing Phenylpropanoids

R1O DDQ (2.2 equiv)H2O

R1O

CHO

OMe

O

OMe

O

CHO

· highly selective mono-oxidation· useful synthetic strategy

metal-free

· metal-free and mild conditions· useful in phenylpropanoids synthesis· gram-scale synthesis

7 examples63–76% yield

DDQ

single product, 66% yield

+

Paper

4611

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Synthesis 2018, 50, 4617–4626DOI: 10.1055/s-0037-1610252

G. ToyookaA. TujiK.-i. Fujita*Kyoto University, Japan

as

Efficient and Versatile Catalytic Systems for the N-Methylation of Primary Amines with Methanol Catalyzed by N-Heterocyclic Carbene Complexes of Iridium

Ir NH3NH3

N

N

R

R

cat. 2+

Alk NH2

Ar NH2

Ir-NHC cat.

50 to 90 °CMeOH

K2CO3

120 °C

Alk NMe

Me

Ar NMe

H

Ar NMe

Me

Ir-NHC cat.K2CO3

Ir-NHC cat.

+

MeOH+

Ir Cl

ClN

N

R

R

cat.

Paper

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Synthesis 2018, 50, 4627–4636DOI: 10.1055/s-0037-1610536

Z.-H. YangJ.-N. ZhuZ.-H. JinJ. ZhengS.-Y. Zhao*Donghua University, P. R. of ChinaShanghai Institute of Organic Chemistry, P. R. of China

Copper-Catalyzed Intermolecular Thioamination of Maleimides with Thiols and Formamides: A One-Step Construction of 3-Amino-4-thio-maleimides Using Formamides as Nitrogen Sources

Unperturbed double bond

R2, R3, R4 = H, aryl, alkylR1 = aryl, alkyl

+

N OO

R2

R1S H

N OO

R2

R1SH

CuI (0.2 equiv)

HBF4, O2, 120 °C+ N

R4

R3

HN

R4

R3H

O

Direct C(sp2)–H bond difunctionalizations

High efficiency and atom economy

High functional-group tolerance

C–S and C–N bond formation in one step

Formamides as the nitrogen sources

23 examples, 27–87% yields

Paper

4627


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Synthesis 2018, 50, 4637–4644DOI: 10.1055/s-0037-1610231

K.-J. LiuX.-L. ZengY. ZhangY. WangX.-S. XiaoH. YueM. WangZ. TangW.-M. He*Hunan University of Science and Engineering, P. R. of China

Syn thesis

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Palladium-Catalyzed Reductive Coupling of Nitroarenes with Phenols leading to N-Cyclohexylanilines

+

HN

NO2R1

R1HOPd/C (10 mol%)

HCO2Na, TFAtoluene, 100 °C

R2

R2

21 examplesup to 92% yield

Paper

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Synthesis 2018, 50, 4645–4650DOI: 10.1055/s-0037-1610537

Y.-Y. LiaoL. XuR.-Y. Tang*W.-X. Zheng*South China Agricultural Univer-sity, P. R. of China

as

Palladium-Catalyzed Selective Synthesis of 3-Hydroxy-2-oxindoles via Cascade C–H Cycloaddition and Oxidation of α-Aminoacetophenones

N

ON

O

HO

R1 R2

R1

R2H

MeMe

H2OPd(OAc)2 (10 mol%)

AgOAc (3 equiv)

MeCN/t-BuOH120 °C, 12 h

15 examples37–69% yields

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Synthesis 2018, 50, 4651–4658DOI: 10.1055/s-0037-1610822

M.-Y. Chang*Y.-S. WuY.-T. HsiaoKaohsiung Medical University, Taiwan

Gram-Scale Synthesis of β-Sulfonyl Styrenes

1,1-diacetoxylation/deacetoxylative sulfonylation

ArArPPA, Ac2O S

O

O

ROAr

OAc

OAc

then NaSO2R

economical and gram-scale synthesis 29 examples 41–93% yields

Paper

4651


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Synthesis 2018, 50, 4659–4667DOI: 10.1055/s-0037-1610652

Y. SatoY. AshidaD. YoshitakeM. HoshinoT. TakemotoY. Tanabe*Kwansei Gakuin University, Japan

Syn thesis

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Stereoretentive Suzuki–Miyaura and Kumada–Tamao–Corriu Cross-Couplings for Preparing (E)- and (Z)-Stereodefined, Fully Substituted α,β-Unsaturated Esters: Application for a Pharmacophore Synthesis

R1

O

R2

CO2Me

R1CO2Me

R2

OTs

R1

OTs

CO2Me

R2

R1CO2Me

R2

Ar (or R)

R1

Ar (or R)

CO2Me

R2

(E)-Enol tosylations

ArB(OH)2 [SM] or RMgBr [KTC]

(Z)-Enol tosylations

cat. Pd(OAc)2, cat. SPhos

C6H4(m-OBn)

CO2Me

Me

C6H4(m-OBn)

Me

CO2Me

Application

Paper

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Synthesis 2018, 50, 4668–4682DOI: 10.1055/s-0037-1609563

G. LiuY. WuJ. HanW. HeJ. ChenH. DengM. ShaoH. Zhang*W. Cao*Shanghai University, P. R. of ChinaShanghai Institute of Organic Chemistry, P. R. of China

as

N-Heterocycle-Triggered MCRs: An Approach to the Concise Synthesis of Perfluoroalkylated Spiro-1,3-oxazines

N

RF CO2Me

N

O

O

R3

N O

NRF

MeO2C

R3

O N O

NRFMeO2C

OHH

R3MeCN

70 °C, 12 hsealed tube

R1

R2

R1 R1

R2 R2

up to 97% total yield22 examples

RF = CF3, C2F5, n-C3F7

Paper

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Synthesis 2018, 50, 4683–4689DOI: 10.1055/s-0037-1609914

R. J. McKinnieT. DarweeshP. A. ZitoT. J. Shields Jr.M. L. Trudell*University of New Orleans, USA

Synthesis of the 5-Fluoro-4-hydroxypentyl Side Chain Metabolites of Synthetic Cannabinoids 5F-APINACA and CUMYL-5F-PINACA

Paper

4683


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Synthesis 2018, 50, 4690–4694DOI: 10.1055/s-0037-1610221

M. KohrU. Kazmaier*Universität des Saarlandes, Germany

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Stereoselective Synthesis of d4-(S)-Lysine from (S)-Serine

Serine

NH2

H2N COOH

DD

DD

BocHN COOMe

I

1) Zn, CuCN iodoalkyne2) D23) deprotection

45%3 steps

Paper

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Errata

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https://doi.org/10.1055/s-0037-1610221

Documents

Imprimatur: Date, Signature tc2318ss.fm 11/15/18 · Efficient and Versatile Catalytic Systems for the N-Methylation of Primary Amines with Methanol Catalyzed by N-Heterocyclic Carbene