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
  • [31] Platinum-Catalyzed Enantioselective Tandem Alkylation/Arylation Phosphines. Asymmetric Synthesis of Primary P-Stereogenic 1-Phosphaacenaphthenes
    Anderson, Brian J.
    Guino-O, Marites A.
    Glueck, David S.
    Golen, James A.
    DiPasquale, Antonio G.
    Liable-Sands, Louise M.
    Rheingold, Arnold L.
    ORGANIC LETTERS, 2008, 10 (20) : 4425 - 4428
  • [32] Diastereoselective Coordination of P-Stereogenic Secondary Phosphines in Copper(I) Chiral Bis(phosphine) Complexes: Structure, Dynamics, and Generation of Phosphido Complexes
    Gibbons, Sarah K.
    Valleau, Christopher R. D.
    Peltier, Jesse L.
    Cain, Matthew F.
    Hughes, Russell P.
    Glueck, David S.
    Golen, James A.
    Rheingold, Arnold L.
    INORGANIC CHEMISTRY, 2019, 58 (13) : 8854 - 8865
  • [33] Synthesis and application of P-stereogenic phosphines as superior reagents in the asymmetric aza-Wittig reaction
    Headley, Catherine E.
    Marsden, Stephen P.
    JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (19): : 7185 - 7189
  • [34] Pd(II)-Catalyzed Enantioselective Synthesis of P-Stereogenic Phosphinamides via Desymmetric C-H Arylation
    Du, Zhi-Jun
    Guan, Jing
    Wu, Guo-Jie
    Xu, Peng
    Gao, Lian-Xun
    Han, Fu-She
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (02) : 632 - 635
  • [35] Nucleophilic Substitution of P-Stereogenic Chlorophosphines: Mechanism, Stereochemistry, and Stereoselective Conversions of Diastereomeric Secondary Phosphine Oxides to Tertiary Phosphines
    Ye, Jing-Jing
    Nie, Shao-Zhen
    Wang, Ji-Ping
    Wen, Jing-Hong
    Zhang, Yu
    Qiu, Mao-Ran
    Zhao, Chang-Qu
    ORGANIC LETTERS, 2017, 19 (19) : 5384 - 5387
  • [36] Synthesis of P-stereogenic phosphorus compounds. Asymmetric oxidation of phosphines under appel conditions
    Bergin, Enda
    O'Connor, Cormac T.
    Robinson, Shane B.
    McGarrigle, Eoghan M.
    O'Mahony, Colm P.
    Gilheany, Declan G.
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (31) : 9566 - +
  • [37] Asymmetric synthesis and coordination chemistry of bidentate P-stereogenic phosphines containing ester and thionoester functionalities
    Qin, Y
    Lang, HF
    Vittal, JJ
    Tan, GK
    Selvaratnam, S
    White, AJP
    Williams, DJ
    Leung, PH
    ORGANOMETALLICS, 2003, 22 (19) : 3944 - 3950
  • [38] Enantioselective synthesis of P-stereogenic allenylphosphines through Ni-catalysed propargylic substitution
    Wei-Han Wang
    Yue Wu
    Hai-Tao Wang
    Peng-Jia Qi
    Wen-Ning Lan
    Qing-Wei Zhang
    Nature Synthesis, 2022, 1 : 738 - 747
  • [39] Synthesis of P-stereogenic phosphonothioates via alcoholysis of phosphonothioates with a binaphthyl group
    Kuwabara, Kazuma
    Maekawa, Yuuki
    Ebihara, Masahiro
    Maruyama, Toshifumi
    Murai, Toshiaki
    HETEROATOM CHEMISTRY, 2018, 29 (5-6)
  • [40] Enantioselective synthesis of P-stereogenic allenylphosphines through Ni-catalysed propargylic substitution
    Wang, Wei-Han
    Wu, Yue
    Wang, Hai-Tao
    Qi, Peng-Jia
    Lan, Wen-Ning
    Zhang, Qing-Wei
    NATURE SYNTHESIS, 2022, 1 (09): : 738 - 747
12345