Metalated nitriles:: Halogen-metal exchange with α-halonitriles

被引：21

作者：

Fleming, FF ^{[1
]}

Zhang, ZY

Knochel, P

机构：

[1] Duquesne Univ, Dept Chem & Biochem, Pittsburgh, PA 15282 USA

[2] Univ Munich, Dept Chem, D-81377 Munich, Germany

来源：

ORGANIC LETTERS | 2004年 / 6卷 / 04期

关键词：

D O I：

10.1021/ol036202s

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

alpha-Halonitriles react with organometallic reagents in a facile halogen-metal exchange. The halogen-metal exchange is extremely fast with Grignard and alkyllithium reagents, generating metalated nitriles in situ with aldehyde, ketone, acid chloride, and acyl cyanide electrophiles. Sequential halogen-metal exchange and methylation of conformationally constrained nitriles is highly stereoselective and consistent with a retentive alkylation of a C-magnesiated nitrile.

引用

页码：501 / 503

页数：3

共 35 条

[1] The development and use of ketene equivalents in [4+2] cycloadditions for organic synthesis [J].

Aggarwal, VK ;

Ali, A ;

Coogan, MP .

TETRAHEDRON, 1999, 55 (02) :293-312

[2] PREPARATION OF ENOLATES FROM ALPHA-HALOKETONES WITH N-BULI, PHMGBR, OR ET(2)ZN VIA HALOGEN-METAL EXCHANGE-REACTION [J].

AOKI, Y ;

OSHIMA, K ;

UTIMOTO, K .

CHEMISTRY LETTERS, 1995, (06) :463-464

[3]

Arseniyadis S., 1984, ORG REACTIONS, V31, P1, DOI DOI 10.1002/0471264180.OR031.01

[4]

Basu A, 2002, ANGEW CHEM INT EDIT, V41, P717

[5] X-RAY STRUCTURE DETERMINATION OF [1-CYANO-2,2-DIMETHYLCYCLOPROPYLLITHIUM-TETRAHYDROFURAN]INFINITY - A TETRAHEDRAL ANIONIC ALPHA-CYANO CARBON-ATOM [J].

BOCHE, G ;

HARMS, K ;

MARSCH, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (20) :6925-6926

[6] THE STRUCTURE OF LITHIUM COMPOUNDS OF SULFONES, SULFOXIMIDES, SULFOXIDES, THIOETHERS AND 1,3-DITHIANES, NITRILES, NITRO-COMPOUNDS AND HYDRAZONES [J].

BOCHE, G .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1989, 28 (03) :277-297

[7]

Boudier A, 2000, ANGEW CHEM INT EDIT, V39, P4414, DOI 10.1002/1521-3773(20001215)39:24<4414::AID-ANIE4414>3.0.CO

[8]

2-C

[9] t-BuOK-Catalyzed addition of ketones and nitriles to vinylic silanes, phosphines and thio derivatives [J].

Bunlaksananusorn, T ;

Rodriguez, AL ;

Knochel, P .

CHEMICAL COMMUNICATIONS, 2001, (08) :745-746

[10] Configurational stability of chiral lithiated cyclopropylnitriles: A density functional study [J].

Carlier, PR .

CHIRALITY, 2003, 15 (04) :340-347

← 1 2 3 4 →