First resolution of a free secondary phosphine chiral at phosphorus and stereospecific formation and structural characterization of a homochiral secondary phosphine-borane complex

被引：43

作者：

Bader, A ^{[1
]}

Pabel, M ^{[1
]}

Willis, AC ^{[1
]}

Wild, SB ^{[1
]}

机构：

[1] AUSTRALIAN NATL UNIV,RES SCH CHEM,INST ADV STUDIES,CANBERRA,ACT 0200,AUSTRALIA

来源：

INORGANIC CHEMISTRY | 1996年 / 35卷 / 13期

关键词：

D O I：

10.1021/ic951494h

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The Rp diastereomer of (-)-menthylmesitylphosphine, (Rp)-1, has been isolated with high configurational purity at phosphorus by fractional crystallization of an (Rp)-1/(Sp)-1 = 43/57 mixture from acetonitrile containing a trace of sodium acetylacetonate as a proton scavenger or by deboranation of the corresponding borane complex (Sp)-2 with diethylamine, thereby effecting the first resolution of a secondary phosphine chiral at phosphorus. The crystal and molecular structure of (Sp)-2 has been determined. The ready isolation of (Sp)-2 of 97% diastereomeric purity in 66% yield from an equilibrium (Rp)-2/(Sp)-2 = 28/72 mixture in n-hexane by second-order asymmetric transformation and its quantitative and stereospecific conversion under mild conditions into (Rp)-1 of similar purity augurs well for the future of the resolved secondary phosphines in stereoselective syntheses.

引用

页码：3874 / 3877

页数：4

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