Highly (≥98 %) Selective Trisubstituted Alkene Synthesis of Wide Applicability via Fluoride-Promoted Pd-Catalyzed Cross-Coupling of Alkenylboranes

被引：15

作者：

Negishi, Ei-ichi ^{[1
]}

Tobrman, Tomas ^{[1
]}

Rao, Honghua ^{[1
]}

Xu, Shiqing ^{[1
]}

Lee, Ching-Tien ^{[1
]}

机构：

[1] Purdue Univ, Herbert C Brown Labs Chem, W Lafayette, IN 47907 USA

来源：

ISRAEL JOURNAL OF CHEMISTRY | 2010年 / 50卷 / 5-6期

基金：

美国国家卫生研究院;

关键词：

alkene synthesis; bromoboration; cross-coupling; F-promoted alkenylation; (Z)-beta-bromo-1-alkenyl(pinacol)borane; STEREOSELECTIVE-SYNTHESIS; CONTROLLED CARBOMETALATION; ARYLBORONIC ACIDS; HALOBORATION; ARYL; EFFICIENT; ROUTE; CARBOALUMINATION; DERIVATIVES; ACETYLENES;

D O I：

10.1002/ijch.201000051

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Z)-beta-bromo-1-propenyl(pinacol)borane (4), recently made available in 85% yield as a >= 98% isomerically pure compound via bromoboration of 1-propyne, has been converted to beta-alkyl-, aryl-, and alkenyl-substituted (Z)-2-methyl-1-alkenyl(pinacol)boranes (2a) in ca. 75% yield based on propyne via Pd-catalyzed Negishi alkenylation with suitable organozinc bromide. The previously sluggish and modest-yielding Suzuki alkenylation of beta,beta-disubstituted alkenylboranes has been significantly promoted by fluorides, especially nBu(4)NF(TBAF) or CsF, to give trisubstituted alkenes, i.e., (Z)-beta-Me-substituted 3-i-3-xi and (E)-beta-Ph-substituted 2b-i and 2b-ii. In all cases, each alkene product was formed in a >= 98% stereoselectivity. The propyne-based protocol nicely complements the widely used Zr-catalyzed alkyne methylalumination-Pd-catalyzed alkenylation by providing a highly stereoselective(>= 98%) route to (Z)-Me-substituted alkenes.

引用

页码：696 / 701

页数：6

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