Chiral organotin hydrides containing intramolecular coordinating substituents

被引：33

作者：

Dakternieks, D ^{[1
]}

Dunn, K

Schiesser, CH

Tiekink, ERT

机构：

[1] Deakin Univ, Ctr Chiral & Mol Technol, Geelong, Vic 3217, Australia

[2] Univ Melbourne, Sch Chem, Parkville, Vic 3052, Australia

[3] Univ Adelaide, Dept Chem, Adelaide, SA 5005, Australia

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2000年 / 605卷 / 02期

基金：

澳大利亚研究理事会;

关键词：

chiral; organotin; hydride;

D O I：

10.1016/S0022-328X(00)00315-6

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A series of chiral non-racemic triorganotin halides and triorganotin hydrides containing one or two (1R,2S,5R)-menthyl (Men) substituents as well as the 8-dimethylaminonaphthyl (L) or 2-[(1,6)-1-dimethylaminoethyl]phenyl (L*) substituents has been synthesised and characterised. Each of the compounds MenPhLSnBr (1) and :MenPhLSnH (2) has a stereogenic tin centre and the compounds were isolated in diastereomeric ratios of 60:40 and 66:33, respectively. Compounds MenPhL*SnCl (3) and MenPhL*SnH (4) were synthesised with diastereomeric ratios of 73:27 and 64:36, respectively. Single crystal X-ray analysis of MenPhL*SnCl (3), Men(2)L*SnCl (8), and MenPh(2)LSn (10) reveals that each structure has a tendency towards penta-coordination at the tin centre as a result of intramolecular N-->Sn interactions. AM1 calculations successfully predict the molecular geometries observed in the solid state as well as the diastereomeric ratios observed in solution. (C) 2000 Elsevier Science S.A. All rights reserved.

引用

页码：209 / 220

页数：12

共 25 条

[1]

BEURSKENS PT, 1994, DIRDIF PROGRAM SYSTE

[2] Enantioselective hydrogen transfer from a chiral tin hydride to a prochiral carbon-centered radical [J].

Blumenstein, M ;

Schwarzkopf, K ;

Metzger, JO .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1997, 36 (03) :235-236

[3] Organostannanes derived from(-)-menthol:: Controlling stereochemistry during the preparation of (1R,2S,5R)-menthyldiphenyltin hydride and bis((1R, 2S,5R)-menthyl)phenyltin hydride [J].

Dakternieks, D ;

Dunn, K ;

Henry, DJ ;

Schiesser, CH ;

Tiekink, ERT .

ORGANOMETALLICS, 1999, 18 (17) :3342-3347

[4] Stannanes as free-radical reducing agents: an ab initio study of hydrogen atom transfer from some trialkyltin hydrides to alkyl radicals [J].

Dakternieks, D ;

Henry, DJ ;

Schiesser, CH .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1997, (09) :1665-1669

[5] Remarkable Lewis acid mediated enhancement of enantioselectivity during free-radical reductions by simple chiral non-racemic stannanes [J].

Dakternieks, D ;

Dunn, K ;

Perchyonok, VT ;

Schiesser, CH .

CHEMICAL COMMUNICATIONS, 1999, (17) :1665-1666

[6] Equilibria in free-radical chemistry: An ab initio study of hydrogen atom transfer reactions between silyl, germyl, and stannyl radicals and their hydrides [J].

Dakternieks, D ;

Henry, DJ ;

Schiesser, CH .

ORGANOMETALLICS, 1998, 17 (06) :1079-1084

[7]

Davies A.G., 1997, ORGANOTIN CHEM

[8] GROUND STATES OF SIGMA-BONDED MOLECULES .14. APPLICATION OF ENERGY PARTITIONING TO MINDO/2 METHOD AND A STUDY OF COPE REARRANGEMENT [J].

DEWAR, MJS ;

LO, DH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1971, 93 (26) :7201-&

[9] ENERGY PARTITIONING WITH CNDO METHOD [J].

FISCHER, H ;

KOLLMAR, H .

THEORETICA CHIMICA ACTA, 1970, 16 (03) :163-&

[10] SYNTHESIS OF "8-(DIMETHYLAMINO)-1-NAPHTHYLLITHIUM ETHERATE - ITS STRUCTURE IN THE SOLID (X-RAY) AND IN SOLUTION (LI-7 AND H-1-NMR) [J].

JASTRZEBSKI, JTBH ;

VANKOTEN, G ;

GOUBITZ, K ;

ARLEN, C ;

PFEFFER, M .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1983, 246 (03) :C75-C79

← 1 2 3 →