Intermolecular hydrophosphination of alkynes and related carbon-carbon multiple bonds catalyzed by organoytterbiums

被引：102

作者：

Takaki, K ^{[1
]}

Koshoji, G ^{[1
]}

Komeyama, K ^{[1
]}

Takeda, M ^{[1
]}

Shishido, T ^{[1
]}

Kitani, A ^{[1
]}

Takehira, K ^{[1
]}

机构：

[1] Hiroshima Univ, Grad Sch Engn, Dept Chem & Chem Engn, Higashihiroshima 7398524, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 17期

关键词：

D O I：

10.1021/jo030163g

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Intermolecular hydrophosphination of alkynes with diphenylphosphine is catalyzed by a Yb-imine complex, [Yb(eta(2)-Ph2CNPh)(hmpa)(3)], to give alkenylphosphines and phosphine oxides after oxidative workup in good yields under mild conditions. This reaction is also applicable to various carbon-carbon multiple bonds such as conjugated diynes and dienes, allenes, and styrene derivatives. Regio- and stereoselectivity and the scope and limitation of the present reaction clearly differ from those of the corresponding radical reaction. Instead, the reaction takes place through insertion of alkynes to a Yb-PPh2 species, followed by protonation. In fact, the Yb-phosphido complex, [Yb(PPh2)(2-)(hmpa)(3)], is obtained from the imine complex and phosphine, which exhibits similar catalyst activity for the hydrophosphination. The empirical rate law is v = k [catalyst](2) [alkyne](1) [phosphine](0) at least under the standard conditions.

引用

页码：6554 / 6565

页数：12

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