Recent Developments in Alkynylationweb.pkusz.edu.cn › huang › files › 2013 › 04 ›...

Reporter: Zhao-feng Wang

Supervisor: Yong Huang

2013-03-27

Recent Developments in Alkynylation

--New approaches to introduce an alkynyl group

Contents

1. Introduction of Acetylene Chemistry

2. Nucleophilic alkynylation : Classic text book approach

3. Electrophilic alkynylation : The dark side of acetylene chemistry

4. Radical C-alkynylation

5. Summary and outlook

Introduction -- Structure and Bonding

Linear Acetylenic Scaffolds

Picture downloaded from http://en.wikipedia.org

Introduction -- Why we need to introduce an alkynyl group?

Tykwinsky, R. R. et al. Synlett 2004, 182-184.

Q. Lin et al. Chem. Commun. 2010, 46, 1589-1600

Contents

Nucleophilic alkynylation: Classic text book approach

Addition of Alkyne Nucleophiles to Carbonyl Groups

Sonogashira coupling of aryl halides and acetylenes

J. Waser et al. Chem. Soc. Rev. 2012, 41, 4165–4179

Combined enantioselective Brønsted acid and metal-catalyzed alkynylation of

α-imino esters

Nucleophilic alkynylation

M. Rueping et al. Angew. Chem., Int. Ed. 2007, 46, 6903-6906

Asymmetric alkynylation of α-imino esters via synergistic catalysis strategy

Sonogashira coupling of aryl halides and acetylenes

Nucleophilic alkynylation

Innovative improvement of Sonogashira coupling

M. Eckhardt, G.-C. Fu et al. J. Am. Chem. Soc. 2003, 125, 13642-13643

The first applications of carbene ligands in sonogashira reactions of

unactivated alkyl halides

Contents

Electrophilic alkynylation : The dark side of acetylene chemistry

Electrophilic alkynylation reagents

Addition of alkynes on a nucleophilic position

J. Waser et al. Chem. Soc. Rev. 2012, 41, 4165–4179

Electrophilic alkynylation : Heteroatom alkynylation

P. J. Stang et al. Synthesis 1994,1255–1256

K. S. Feldmen et al. J. Org. Chem.1996, 61, 5440–5452

A. T. Stengel et al. Angew. Chem., Int. Ed. 1998, 37,489–492

C-N bond formation: first ynamine synthesis

Extended methodology to ynamide and proposed mechanism

C-S bond formation: regiospecific thiazole synthesis using alkynyliodonium salts

P. Wipf et al. J. Org. Chem. 1996, 61, 8004–8005

M. Ochiai et al. Angew. Chem., Int. Ed. 2005, 44, 6896–6899

Electrophilic alkynylation : Heteroatom alkynylation

S. A. Galton et al. J. Org. Chem. 1965, 30, 1930–1934

J. Waser et al. Chem.–Eur. J. 2010, 16, 9457–9461

Electrophilic alkynylation : Enolate alkynylation

First alkynyliodonium salt reacted with the enolate

Improvement of the methodology involving novel hypervalent iodine reagents

A. S. Kende et al. J. Am. Chem. Soc.1984, 106, 3551–3562

A. J. T. Pinhey et al. J. Chem. Soc. Perkin Trans. 1, 1997, 1465–1468.

Alkynylation of non-stabilized enolates using chloroacetylenes

K. A. Jørgensen et al. J. Am. Chem. Soc. 2007, 129, 441-449

Highly enantioselective electrophilic alkynylation

Electrophilic alkynylation : Alkynylation of organometallic nucleophiles

Pioneering work using alkynyl sulfones

Efficient synthesis of aliphatic acetylenes based on a mixed Zn–Cu reagent

Organocopper reagent as nucleophile in total synthesis

W. E. Truce et al. J. Org. Chem. 1979, 44, 3444–3445

P. Knochel et al. Tetrahedron Lett. 1989, 30,4799–4802.

P. S. Baran et al. J. Am.Chem. Soc. 2010, 132, 7119–7137.

Cadiot–Chodkiewicz alkynylation of terminal alkynes

Electrophilic alkynylation : Alkynylation of C(sp)–H

Palladium could be a superior catalyst

W. Chodkiewicz et al. Hebd. Seances Acad. Sci.1955, 241, 1055–1057.

A.-W. Lei et al. J. Am. Chem. Soc. 2008, 130, 14713–14720

Gold-catalyzed alkynylation of indoles and pyrroles using alkynyl benziodoxolone

Electrophilic alkynylation : Alkynylation of C(sp2)–H

J. Waser et al. Angew. Chem., Int. Ed. 2009, 48, 9346–9349

Electrophilic alkynylation : Alkynylation of C(sp3)–H

First Palladium(II)-catalyzed β-C(sp3)−H bond alkynylation

Palladium(0)-catalyzed primary β-C(sp3)−H bond alkynylation

N. Chatani et al. J. Am. Chem. Soc. 2011, 133, 12984–12986

J.-Q. Yu et al. J. Am. Chem. Soc. 2013, 135 , 3387–3390

Contents

Radical C-alkynylation

G. A. Russell et al. Tetrahedron Lett. 1986, 27, 3479-3482

P. L. Fuchs et al. J. Am. Chem. Soc. 1996, 118, 4486-4487

P. Renaud et al. Angew. Chem., Int. Ed. 2006, 45, 5847-5849

C.-Z. Li et al. J. Am. Chem. Soc. 2012, 134, 14330−14333

Overview of radical C-alkynylation reactions

Radical C-alkynylation

Radical-mediated C(sp3) - C(sp) coupling

C.-Z. Li et al. J. Am. Chem. Soc. 2012, 134, 14330−14333

Summary

Acknowledgement

Prof. Yong Huang

All the members in SCBB

All my labmates in E201

Thank you!

Supporting information

General Procedures for the Coupling Reactions. To an ovendried Schlenk tube with a magnetic stir bar were added Pd(dba)2

(11.5 mg, 0.02 mmol), L1 ligand (7.9 mg, 0.02 mmol), and CuI

(1.9 mg, 0.01 mmol). DMF (1 mL) was added via a syringe. The

system was vacuumed with an oil pump at 0 °C and filled with

nitrogen, and this was repeated five times. After the mixture was

stirred under nitrogen for about 10 min, alkyne (0.6 mmol) was

added via a microliter and stirred for another 5 min. 1-Bromoalkyne

was added last via a microliter syringe. The system was stirred at

room temperature for 10 h. Upon completion, 4 mL of brine was

added, and the mixture was extracted by ethyl acetate (3 mL × 3).

The product was obtained by flash column chromatography.

Supporting information

Recent Developments in Alkynylationweb.pkusz.edu.cn › huang › files › 2013 › 04 ›...

Documents

Supporting information for Preparation and study of an f,f,f’,f’’ … · 2012-12-07 · methanol. CuSO4 5H2O (4.8 mg, 0.02 mmol) and sodium ascorbate (8mg, 0.04 mmol) are then

QO-RES-06-2020-000691.R1 revised SI · To a 50 mL dry flask were added alkene (5.0 mmol), 2 (915 mg, 7.5 mmol), TMSCl(1.65 mL, 15 mmol), CuSO4•5H2O (125 mg, 0.50 mmol) and MeCN

Journal of Materials Chemistry C - Indian Institute of ...iitg.ac.in/stud/h.sameer/Anamika.pdf · (260 mg, 1.67 mmol) and/or octyl amine (216 mg, 1.67 mmol), zinc acetate (catalytic

Electronic Supplementary Information · Sb3LMe2Cl3 Synthesis A solution of H3LMe (12.1 mg, 0.05 mmol) in TCE (2 mL) was combined with a solution of SbCl3 (26.7 mg, 0.12 mmol) in TCE

Supporting Information Fructose-coated Nanoparticles: a ... · 2,3:4,5-di-O-isopropylidene-β-D-fructopyranose (1 g, 1.83 mmol), AIBN (0.8 mg, 4.8 × 10-3 mmol) and CPADB (10 mg,

03990 5 mg 3.4 mg 0.02 rnL (Irv30 oc) . 01 (20161ã 20P) LHSQ … · 2018. 9. 4. · 03990 5 mg 3.4 mg 0.02 rnL (Irv30 oc) . 01 (20161ã 20P) LHSQ ()l-h 26 a031-629-8690 GCTHIOCTICACID

Starting your journey - OneTouch® · 80–130 mg/dL * (4.4–7.2 mmol/L) After meal blood sugar < 180 mg/dL * ( 10.0 mmol/L) Blood sugar target for non-pregnant adults: 6 *Always

A Novel Reactive Turn-On Probe Capable of Selective ...To a stirred solution of S7 (17 mg, 0.05 mmol) in 2 mL DMF was added HATU (23 mg, 0.06 mmol), S1 (20 mg, 005 mmol) and TEA (0.02

A Flexible Approach to Pd Catalyzed Carbonylations via ... · was charged with aroyl-DMAP salt 2a (177 mg, 0.50 mmol) and diisopropylethylamine (129 mg, 1.0 mmol) in dichloromethane

Supplementary Online Content...defined on the basis of a fasting glucose level ≥7.0 mmol/L (≥126 mg/dL), or non-fasting plasma glucose levels ≥11.1 mmol/L (≥200 mg/dL) if fasting

Robust Metal Triazolate Frameworks for CO Capture from ...€¦ · Synthesis of ZnF(TZ): A mixture of Zn(NO3)2ꞏ6H2O (223.1 mg, 0.75 mmol), HTZ (51.8 mg, 0.75 mmol), hydrofluoric

Electronic Supplementary Information · The mixture of commercial benzyl alcohol 1a (0.93 mL, 9 mmol), phenylacetone 6a (360.5 mg, 3 mmol), Cu(OAc)2.H2O (6 mg, 0.03 mmol, 1 mol%)

Blue electrophosphorescent organoplatinum(II) complexes with … · 2011-07-13 · 2-bromoanisole (1.25 mL, 10 mmol), KOH (1.12 g, 20 mmol) and Cu2O (280 mg, 2 mmol) under nitrogen

Supporting Information Graphene Frameworks and OER ... · synthesis conditions. More specifically, in order to form PNGF_DAP or PNGF_ADP, 396 mg DAP (3 mmol) or 345 mg ADP (3 mmol)

Amides Nickel/Briphos-Catalyzed Transamidation of ...H O O M e N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and 4-methoxyaniline (49 mg, 0.4 mmol) provided 3ae (35 mg, 78 %). Yellow

Facile “Click” to Fabricate a FRET-Based · 2014. 4. 29. · A slurry of 3 (100 mg, 0.20 mmol), 4 (35 mg, 0.20 mmol), CuI (3.8 mg, 0.02 mmol ) and N,N-diisopropylethylamine (26

diffractometer. 1H-NMR and C-NMR spectra were obtained on a … · To a mixtureof Eu(NO3)3•6H2O (0.0044 mmol, 2 mg), Tb(NO3)3•6H2O (0.20 mmol, 88 mg) and H6L1 (0.010 mmol, 10

Supporting information Simple Synthesis and Molecular ... · palladium acetate (0.02 g, 0.10 mmol), tri-tert-butylphosphine (0.04 g, 0.20 mmol) and sodium tert-butoxide (0.48 g, 4.97

NUOVA NOTA 13 ALGORITMO APPLICATIVO. mg/dL cholesterol = mmol/L × 38.6 mg/dL triglycerides = mmol/L × 88.5 mg/dL glucose = mmol/L × 18 Particolari categorie

Mg−Mg-bonded compounds with N,N -dipp-substituted ... · tBuNCO (29 µL, ca. 25 mg, 0.25 mmol) was added to a cooled (–40°C) solution of in situ prepared compound 3 (0.12 mmol)