Nonracemic Allylic Boronates through Enantiotopic-Group-Selective Cross-Coupling of Geminal Bis(boronates) and Vinyl Halides

被引：160

作者：

Potter, Bowman ^{[1
]}

Szymaniak, Adam A. ^{[1
]}

Edelstein, Emma K. ^{[1
]}

Morken, James P. ^{[1
]}

机构：

[1] Boston Coll, Dept Chem, Merkert Chem Ctr, Chestnut Hill, MA 02467 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 52期

关键词：

QUATERNARY STEREOGENIC CENTERS; STEREOSELECTIVE-SYNTHESIS; ESTERS; CARBON; CONSTRUCTION; DIBORYLATION; SUBSTITUTION; ALLYLATION; ALCOHOLS; BONDS;

D O I：

10.1021/ja510266x

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Under the influence of a chiral palladium catalyst, 1,1-bis(pinacolboronate) esters undergo asymmetric cross-coupling with bromoalkenes to generate nonracemic allyl boronates with high levels of enantioselectivity. The so-formed allyl boronates may be oxidized with hydrogen peroxide to provide secondary allylic alcohols or with nitrosobenzene to furnish nonracemic tertiary allylic alcohols. Mechanistic experiments suggest the operation of a pathway involving outer-sphere stereoinvertive transmetalation.

引用

页码：17918 / 17921

页数：4

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