Addition reaction of vinylic reagents, derived from α-chloroenones, to carbonyl compounds promoted by samarium diiodide

被引：12

作者：

Concellón, JM

Bernad, PL

Huerta, M

García-Granda, S

Díaz, MR

机构：

[1] Univ Oviedo, Fac Quim, Dept Quim Organ & Inorgan, E-33071 Oviedo, Spain

[2] Univ Oviedo, Fac Quim, Dept Quim Fis & Analit, E-33071 Oviedo, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2003年 / 9卷 / 21期

关键词：

Baylis-Hillman reaction; diastereoselectivity; nucleophilic addition; samarium; vinyl reagents;

D O I：

10.1002/chem.200304954

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A new samarium diiodide-promoted addition reaction of vinylsamarium reagents, derived from (Z)-alpha-chloro-alpha,beta-unsaturated phenones 1, to both ketones (in THF) and aldehydes (in acetonitrile) led to (Z)-2-(1-hydroxyalkyl)-2,3-unsaturated ketones in good yield. These transformations took place with total or very high inversion of the stereochemistry of the C=C double bond of the starting chloroenone, producing the Z diastereoisomer. A new methodology to prepare SmI2 in acetonitrile by sonic treatment of 1,2-diiodoethane with Sm powder is also described. A mechanism to explain this transformation is proposed.

引用

收藏

页码：5343 / 5347

页数：5

相关论文

共 27 条

[1] The Baylis-Hillman reaction: A novel carbon-carbon bond forming reaction [J].

Basavaiah, D ;

Rao, PD ;

Hyma, RS .

TETRAHEDRON, 1996, 52 (24) :8001-8062

[2] A new protocol for the syntheses of (E)-3-benzylidenechroman-4-ones:: a simple synthesis of the methyl ether of bonducellin [J].

Basavaiah, D ;

Bakthadoss, M ;

Pandiaraju, S .

CHEMICAL COMMUNICATIONS, 1998, (16) :1639-1640

[3] SMI2-MEDIATED CYCLIZATION OF VINYL RADICALS [J].

CAPELLA, L ;

MONTEVECCHI, PC .

TETRAHEDRON LETTERS, 1994, 35 (45) :8445-8448

[4] CYCLIZATIONS AND REARRANGEMENTS OF SAMARIUM DIIODIDE-GENERATED VINYL RADICALS [J].

CAPELLA, L ;

MONTEVECCHI, PC ;

NAVACCHIA, ML .

JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (23) :7424-7432

[5] Very rapid preparation of SmI2 by sonic treatment of iodoform and metallic samarium [J].

Concellón, JM ;

Rodríguez-Solla, H ;

Bardales, E ;

Huerta, M .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2003, 2003 (09) :1775-1778

[6] Preparation of (Z)-α-chloro-α,β-unsaturated ketones with total or high diastereoselectivity [J].

Concellón, JM ;

Huerta, M .

TETRAHEDRON, 2002, 58 (39) :7775-7780

[7] Iodomethylation of chiral alpha-amino aldehydes by means of samarium/diiodomethane. Application to the synthesis of various enantiomerically pure compounds [J].

Concellon, JM ;

Bernad, PL ;

PerezAndres, JA .

JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (25) :8902-8906

[8] Samarium diiodide-promoted diiodomethylation of carbonyl compounds with iodoform.: Synthetic applications of diiodoalcohols [J].

Concellón, JM ;

Bernad, PL ;

Pérez-Andrés, JA .

TETRAHEDRON LETTERS, 1998, 39 (11) :1409-1412

[9] SYNTHETIC POTENTIAL OF THE TERTIARY-AMINE-CATALYSED REACTION OF ACTIVATED VINYL CARBANIONS WITH ALDEHYDES [J].

DREWES, SE ;

ROOS, GHP .

TETRAHEDRON, 1988, 44 (15) :4653-4670

[10] Effective enantioselective approach to alpha-aminoalkylacrylic acid derivatives via a synthetic equivalent of an asymmetric Baylis-Hillman reaction: Application to the synthesis of two C-2' hydroxymethyl analogues of docetaxel [J].

Genisson, Y ;

Massardier, C ;

GautierLuneau, I ;

Greene, AE .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1996, (24) :2869-2872