Thermodynamic Control of 1,3-Boratropic Shifts of α- and γ-Stannyl-Substituted Allylboranes: Hyperconjugation Outweighs Steric Effects

被引：18

作者：

Stewart, Preston S. ^{[2
]}

Chen, Ming ^{[1
]}

Roush, William R. ^{[1
]}

Ess, Daniel H. ^{[2
]}

机构：

[1] Scripps Florida, Dept Chem, Jupiter, FL 33458 USA

[2] Brigham Young Univ, Dept Chem & Biochem, Provo, UT 84602 USA

来源：

ORGANIC LETTERS | 2011年 / 13卷 / 06期

关键词：

STEREOSELECTIVE-SYNTHESIS; ASYMMETRIC-SYNTHESIS; GEOMETRIC ISOMERS; POSITIVE CHARGE; SILICON; GERMANIUM; STABILIZATION; HYDROBORATION; ALDEHYDES; ALCOHOLS;

D O I：

10.1021/ol2001599

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

(E)-delta-Stannyl homoallylic alcohols are prepared by an allene hydroboration-aldehyde allylboration sequence (Chen, M. et al. J. Am. Chem. Soc. 2010, 132, 7881). Key to this reaction sequence is that the kinetic allene hydroboration product, 2a, is less stable than and isomerizes to the more sterically congested alpha-stannylallylborane 3a (see abstract figure). An M06-2X density functional analysis shows that the C-Sn to boron sigma-pi hyperconjugation interaction is sufficiently stabilizing to override the steric congestion in 3a.

引用

页码：1478 / 1481

页数：4

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