Development of ruthenium catalysts for the enantioselective synthesis of P-stereogenic phosphines via nucleophilic phosphido intermediates

被引：0
|
作者：
Chan, Vincent S. [1 ]
Chiu, Melanie [1 ]
Bergman, Robert G. [1 ]
Toste, F. Dean [1 ]
机构：
[1] Department of Chemistry, University of California, Berkeley, CA 94720, United States
来源：
Journal of the American Chemical Society | 2009年 / 131卷 / 16期
关键词：
This work details the development of ruthenium(ll) catalysts for the enantioselective alkylation of chiral racemic secondary phosphines. The reactions proceed through the intermediacy of nucleophilic phosphido species; which have low barriers to pyramidal inversion; this allows for a dynamic kinetic asymmetric alkylation. The initially discovered [((R)-/Pr-PHOX) 2Ru(H)][BPh 4] (6) catalyst was found to be effective in the reaction with benzylic chlorides; moreover, the alkylation displayed an unusual temperature dependence. However, the limited scope of alkylation of 6 motivated further studies which led to the development of two complementary chiral mixed ligand Ru(ll) catalysts of type [L 1L 2Ru(H)] +. These catalysts were derived from a combination of one chiral and one achiral ligand, where a synergistic interaction of the two ligands creates an effective asymmetric environment around the ruthenium center. The (R)-MeO-BiPHEP/dmpe (dmpe = 1,2-bis(dimethylphosphino)ethane) catalyst (10) was found to be effective for the asymmetric alkylation of benzylic chlorides, while the (R)-DIFLUORPHOS/dmpe catalyst (11) was optimal for the nucleophilic substitution of less activated alkyl bromides; the scope of the respective catalysts was also explored. © 2009 American Chemical Society;
D O I：
暂无
中图分类号：
学科分类号：
摘要：
Journal article (JA)
引用
收藏
页码：6021 / 6032
相关论文
共 50 条
  • [41] Applications of 31P NMR spectroscopy in development of M(Duphos)-catalyzed asymmetric synthesis of P-stereogenic phosphines (M = Pt or Pd)
    Glueck, David S.
    COORDINATION CHEMISTRY REVIEWS, 2008, 252 (21-22) : 2171 - 2179
  • [42] Ni-catalyzed highly enantioselective synthesis of sulfur protected P-stereogenic supramolecular phosphine
    Vijay S Koshti(S)
    Amol C Chandanshive
    Nilesh R Mote
    Samir H Chikkali
    Journal of Chemical Sciences, 2021, 133
  • [43] Ni-catalyzed highly enantioselective synthesis of sulfur protected P-stereogenic supramolecular phosphine
    Koshti, Vijay S.
    Chandanshive, Amol C.
    Mote, Nilesh R.
    Chikkali, Samir H.
    JOURNAL OF CHEMICAL SCIENCES, 2021, 133 (04)
  • [44] Asymmetric Synthesis of P-Stereogenic Diarylphosphinites by Palladium-Catalyzed Enantioselective Addition of Diarylphosphines to Benzoquinones
    Huang, Yinhua
    Li, Yongxin
    Leung, Pak-Hing
    Hayashi, Tamio
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (13) : 4865 - 4868
  • [45] Stereoselective Catalytic Synthesis of P-Stereogenic Oxides via Hydrogenative Kinetic Resolution
    Fernandez-Perez, Hector
    Vidal-Ferran, Anton
    ORGANIC LETTERS, 2019, 21 (17) : 7019 - 7023
  • [46] Synthesis of P-Stereogenic Benzoazaphosphole 1-Oxides via Alkynylation of P-Stereogenic ortho-Aurated and ortho-Iodo Phosphinic Amides
    Soengas, Raquel
    Belmonte Sanchez, Eva
    Jose Iglesias, Maria
    Lopez Ortiz, Fernando
    ACS OMEGA, 2018, 3 (05): : 5116 - 5124
  • [47] Synthesis of P-stereogenic cyclicphosphinic amides via electrochemically enabled cobalt-catalyzed enantioselective C-H annulation
    Liu, Tao
    Zhang, Wangqin
    Xu, Chao
    Xu, Zhenhui
    Song, Dingguo
    Qian, Wei
    Lu, Gang
    Zhang, Chang-Jun
    Zhong, Weihui
    Ling, Fei
    GREEN CHEMISTRY, 2023, 25 (09) : 3606 - 3614
  • [48] Asymmetric Synthesis of P-Stereogenic Phosphinic Amides via Pd(0)-Catalyzed Enantioselective Intramolecular C-H Arylation
    Liu, Lantao
    Zhang, An-An
    Wang, Yanfang
    Zhang, Fuqiang
    Zuo, Zhenzhen
    Zhao, Wen-Xian
    Feng, Cui-Lan
    Ma, Wenjin
    ORGANIC LETTERS, 2015, 17 (09) : 2046 - 2049
  • [49] Neutral p-cymene ruthenium complexes with P-stereogenic monophosphines. New catalytic precursors in enantioselective transfer hydrogenation and cyclopropanation
    Grabulosa, Arnald
    Mannu, Alberto
    Mezzetti, Antonio
    Muller, Guillermo
    JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2012, 696 (26) : 4221 - 4228
  • [50] Noncovalent Substrate-Directed Enantioselective Heck Reactions: Synthesis of S- and P-Stereogenic Heterocycles
    de Azambuja, Francisco
    Carmona, Rafaela C.
    Chorro, Tomaz H. D.
    Heerdt, Gabriel
    Correia, Carlos Roque D.
    CHEMISTRY-A EUROPEAN JOURNAL, 2016, 22 (32) : 11205 - 11209
12345