摘要：Rajat Shankhdhar,⊥ Sylwia Górczynśka,⊥ Kacper Błaziak, LéonieBlanchard, and Łukasz Woźniak*

转自：康龙化成

Silver(I)-Catalyzed StereochemicalIsomerization of Cyclopropanols

Rajat Shankhdhar,⊥ Sylwia Górczynśka,⊥ Kacper Błaziak, LéonieBlanchard, and Łukasz Woźniak*

⊥R.S. andS.G. contributed equally to thiswork

Faculty of Chemistry, JagiellonianUniversity, Kraków30-387, Poland

—doi.org/10.1021/acs.organomet.4c00432

Recommended by Feng Wang_SC

KEYWORDS:Stereoselective, Isomerization ofCyclopropanols (反应类型),C(sp3)–O (成键类型), cis cyclopropanols (原料), transcyclopropanols(产物), AgOTf (其他)

ABSTRACT: Isomerization of cyclopropane-containing molecules offers a direct pathway to access all of their diastereoisomers. Current catalytic methods, however, are largely confined to isomerization of carbonyl- and vinyl-substituted cyclopropanes. Prof. Woźniak et al. report a catalytic isomerization of cyclopropanols, which converts readily accessible cis-1,2-disubstituted cyclopropanols into their more stable, yet often less accessible, trans-isomers. This enables a straightforward access to both diastereoisomers of these small-ring molecules. Mechanistic studies indicate the catalytic reactivity of silver homo-enolates.

Background and this Work

Mechanism Studies

Summary and comments

In summary, Prof.Woźniak etal. reported a catalyticstereochemical isomerization of cyclopropanols. This study establishes thecatalytic reactivity of silver homoenolates, enabling the conversion of readilyavailable cis-1,2-disubstituted cyclopropanols into their less accessible trans-diastereomers.This provides access to both diastereomers employing a single strategy toconstruct the cyclopropanol core. Mechanistic studies indicate that theisomerization is enantiospeciffc and reversible, favoring the formation of themore stable product. Formation for of the silver homoenolates is supported byexperimental investigations.

来源：新浪财经