Silylcupration of allene with the lower order cuprate (t-BuPh2Si)CuCNLi and reaction with α,β-unsaturated nitriles.: An unusual diaddition process leading to disilyl functionalised ketones

被引：3

作者：

Barbero, A ^{[1
]}

Blanco, Y ^{[1
]}

Fernández, H ^{[1
]}

Pulido, FJ ^{[1
]}

机构：

[1] Univ Valladolid, Dept Quim Organ, E-47011 Valladolid, Spain

来源：

SYNLETT | 2004年 / 15期

关键词：

allenes; silylcupration; allylsilanes; cuprates; regiochemistry;

D O I：

10.1055/s-2004-835643

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The lower order cuprate (t-BuPh2Si)CuCNLi, prepared by mixing one equivalent of t-butyldiphenylsilyllithium and one equivalent of copper(I) cyanide, reacts with allenes in the presence of alpha,beta-unsaturated nitriles showing a regiochemistry that depends on the electronic nature of the nitrile. Electron-poor nitriles give monoadducts (allylsilane containing nitriles) whereas electron-rich nitriles lead to diadducts (allylsilane-vinylsilane containing ketones), the latter resulting from an unusual diaddition (1,2 and 1,4) process. An explanation is advanced and a reliable mechanism proposed.

引用

页码：2833 / 2835

页数：3

共 14 条

[1] Allylsilanes and vinylsilanes from silylcupration of carbon-carbon multiple bonds: Scope and synthetic applications [J].

Barbero, A ;

Pulido, FJ .

ACCOUNTS OF CHEMICAL RESEARCH, 2004, 37 (10) :817-825

[2] Acid-catalyzed cyclization of epoxyallylsilanes.: An unusual rearrangement cyclization process [J].

Barbero, A ;

Castreño, P ;

Pulido, FJ .

ORGANIC LETTERS, 2003, 5 (22) :4045-4048

[3] Intramolecular cyclization of tert-butyldiphenylallylsilane units and carbonyl groups:: Allylsilane terminated cyclization versus the ene reaction [J].

Barbero, A ;

Castreño, P ;

García, C ;

Pulido, FJ .

JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (23) :7723-7728

[4]

Barbero A, 2000, SYNTHESIS-STUTTGART, P1223

[5] A tandem allylsilane-vinylsilane difunctionalization by silylcupration of allene followed by reaction with α,β-unsaturated nitriles [J].

Barbero, A ;

Blanco, Y ;

Pulido, FJ .

CHEMICAL COMMUNICATIONS, 2001, (17) :1606-1607

[6] SYNTHESIS OF VINYLSILANES BY SILYL-CUPRATION OF ACETYLENES USING TERT-BUTYLDIPHENYLSILYL-CUPRATE REAGENTS [J].

BARBERO, A ;

CUADRADO, P ;

FLEMING, I ;

GONZALEZ, AM ;

PULIDO, FJ ;

SANCHEZ, A .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1995, (12) :1525-1532

[7] Functionalised allylsilanes from silylcopper reagents and allene.: A useful strategy for cyclopentane annulations [J].

Barbero, A ;

García, C ;

Pulido, FJ .

TETRAHEDRON, 2000, 56 (18) :2739-2751

[8] THE REACTION OF TERT-BUTYLDIPHENYLSILYCUPRATES WITH ALLENES [J].

BARBERO, A ;

CUADRADO, P ;

GONZALEZ, AM ;

PULIDO, FJ ;

FLEMING, I .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1991, (11) :2811-2816

[9] Silylcupration of allenes followed by reaction with enones.: A new strategy for the synthesis of methylenecyclopentanols [J].

Barbero, A ;

García, C ;

Pulido, FJ .

TETRAHEDRON LETTERS, 1999, 40 (36) :6649-6652

[10] NEW FINDINGS ON THE REGIOCHEMISTRY OF THE SILYLCUPRATION OF ALLENE [J].

BLANCO, FJ ;

CUADRADO, P ;

GONZALEZ, AM ;

PULIDO, FJ ;

FLEMING, I .

TETRAHEDRON LETTERS, 1994, 35 (47) :8881-8882

← 1 2 →