Copper-catalyzed anti-hydrophosphination reaction of 1-alkynylphosphines with diphenylphosphine providing (Z)-1,2-diphosphino-1-alkenes
Copper-catalyzed anti-hydrophosphination reaction of 1-alkynylphosphines with diphenylphosphine providing (Z)-1,2-diphosphino-1-alkenes
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DOI：
10.1021/ja070048d
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发表时间：
2007-04-04
影响因子：
15
通讯作者：
Oshima, Koichiro
中科院分区：
文献类型：
--
作者：
Kondoh, Azusa;Yorimitsu, Hideki;Oshima, Koichiro
在铜催化下，1-炔基膦与二苯基膦的氢化膦化反应以反式方式进行，提供了一种简便、有效的方法制备各种（Z）-1，2-二膦基-1-烯烃及其硫化物。该反应是高度化学选择性的，甚至可以在水性介质中进行。该反应可靠，可实现克级（Z）-1，2-二膦基-1-烯烃的合成。用三（三甲基甲硅烷基）硅烷自由基还原二硫化二膦得到母体三价二膦，而不遭受烯烃几何异构化。通过（Z）-3，3-二甲基-1，2-双（二苯基硫代膦基）-1-丁烯的不对称氢化反应和手性双齿膦配体的双加成反应，合成了一种新的手性双齿膦配体。
Hydrophosphination of 1-alkynylphosphines with diphenylphosphine proceeds in an anti fashion under copper catalysis, providing an easy and efficient access to a variety of (Z)-1,2-diphosphino-1-alkenes and their sulfides. The reaction is highly chemoselective and can be performed even in an aqueous medium. The reaction is reliable enough to realize a gram-scale synthesis of (Z)-1,2-diphosphino-1-alkene. Radical reduction of the diphosphine disulfides with tris(trimethylsilyl)silane yields the parent trivalent diphosphines without suffering from the isomerization of the olefinic geometry. Enantioselective hydrogenation of (Z)-3,3-dimethyl-1,2-bis(diphenylthiophosphinyl)-1-butene followed by desulfidation leads to a new chiral bidentate phosphine ligand.