Studies on the origin of cis-diastereo selectivity of the titanium-mediated cyclopropanation of carboxylic esters with Grignard reagents.: Stereochemistry of the intramolecular cyclization of β-metalloketones

被引：23

作者：

Kananovich, Dmitry G. ^{[1
]}

Kulinkovich, Oleg G. ^{[1
]}

机构：

[1] Belarusian State Univ, Dept Organ Chem, Minsk 220030, BELARUS

来源：

TETRAHEDRON | 2008年 / 64卷 / 07期

关键词：

diastereoselectivity; cyclopropanols; titanacyclopropanes; ate complexes; KULINKOVICH HYDROXYCYCLOPROPANATION; CHEMISTRY; MECHANISM; REACTIVITY; ARYLOXIDE; KETONES; ALPHA; ALKYL; METHYL-D3-PYRIDINES; TITANACYCLOPENTANE;

D O I：

10.1016/j.tet.2007.10.075

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Data on the stereochemistry of the intramolecular cyclization of beta-metaloketones into 1,2-disubstituted cyclopropanols are in agreement with the cyclopropanation of carboxylic esters with alkoxytitanacyclopropane reagents proceeding via the beta-titanoketone inter-mediates with the metal atom bound to a secondary carbon. Hypothesis for the origin of cis-diastereoselectivity of the cyclization of the beta-titanoketones is suggested. It explains the tendency for the preferable formation of cis-1,2-disubstituted cyclopropanols by relief of repulsion strain between the ligands at the octahedral titanium atom. (c) 2007 Published by Elsevier Ltd.

引用

页码：1536 / 1547

页数：12

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