Inoue Hideki, Nagaoka Yasuo, Tomioka Kiyoshi
Graduate School of Pharmaceutical Sciences, Kyoto University,Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.
J Org Chem. 2002 Aug 9;67(16):5864-7. doi: 10.1021/jo025725v.
Upon successive treatment with lithium diisopropylamide and then benzaldehyde, a chiral alpha,beta,psi,omega-unsaturated bisphosphine oxide underwent Michael cyclization-aldol tandem reaction to afford the corresponding endo-alpha,beta-unsaturated cyclic bisphosphine oxides. Sequential stereoselective reduction and Horner-Wadsworth-Emmons olefination gave the corresponding monophosphine oxide. Oxidative conversion of an olefin moiety into a carboxyl group and subsequent deoxygenation of an oxide gave the corresponding chiral phosphinocarboxylic acid, which was successfully applied as a chiral and functionalized monophosphine ligand in a palladium-catalyzed asymmetric allylic alkylation.
在手性α,β,ψ,ω-不饱和双氧化膦先后用二异丙基氨基锂和苯甲醛处理后，发生迈克尔环化-羟醛串联反应，得到相应的内型α,β-不饱和环状双氧化膦。依次进行立体选择性还原和霍纳尔-沃兹沃思-埃蒙斯烯烃化反应，得到相应的单氧化膦。将烯烃部分氧化转化为羧基，随后将氧化物脱氧，得到相应的手性膦羧酸，该手性膦羧酸成功地用作钯催化的不对称烯丙基烷基化反应中的手性官能化单膦配体。
