Asymmetric Induction at Remote Quaternary Centers of Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation

被引：50
|
作者：
Naganawa, Yuki [1 ]
Kawagishi, Mayu [1 ]
Ito, Jun-ichi [1 ]
Nishiyama, Hisao [1 ]
机构：
[1] Nagoya Univ, Grad Sch Engn, Dept Appl Chem, Chikusa Ku, Nagoya, Aichi 4648603, Japan
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 24期
基金：
日本学术振兴会;
关键词：
asymmetric synthesis; desymmetrization; hydrosilylation; quaternary centers; rhodium; ENANTIOSELECTIVE CONSTRUCTION; NATURAL-PRODUCTS; FACILE SYNTHESIS; HECK ARYLATIONS; REDUCTION; DESYMMETRIZATION; ESTERS; TRANSFORMATIONS; STEREOCENTERS; BEARING;
D O I：
10.1002/anie.201601636
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The enantioselective desymmetrizing conjugate hydrosilylation of prochiral differently gamma, gamma-disubstituted cyclohexadienone derivatives 2 to furnish the corresponding cyclohexenones 4 with a remote chiral all-carbon quaternary center at the g position is described. Chiral rhodium-bis(oxazolinyl)-phenyl complexes 1 were effective catalysts for this transformation. This catalytic system was extended to the asymmetric transformation of spirocarbocyclic cyclohexadienones 5 to give the corresponding products 6 with high enantiomeric ratios.
引用
收藏
页码：6873 / 6876
页数：4
相关论文
共 50 条
  • [1] Asymmetric Desymmetrization of Substituted Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation and Theoretical Calculations of Its Mechanistic Aspects
    Naganawa, Yuki
    Ito, Jun-ichi
    Kawagishi, Mayu
    Nishiyama, Hisao
    SYNTHESIS-STUTTGART, 2017, 49 (19): : 4448 - 4460
  • [2] Rhodium-Catalyzed Desymmetric Arylation of γ,γ-Disubsituted Cyclohexadienones: Asymmetric Synthesis of Chiral All-Carbon Quaternary Centers
    Qiao, Yu
    Bai, Shiming
    Wu, Xiao-Feng
    Yang, Ying
    Meng, He
    Ming, Jialin
    ORGANIC LETTERS, 2022, 24 (07) : 1556 - 1560
  • [3] Rhodium-catalyzed asymmetric conjugate alkynylation of nitroalkenes
    Nishimura, Takahiro
    Sawano, Takahiro
    Tokuji, Sumito
    Hayashi, Tamio
    CHEMICAL COMMUNICATIONS, 2010, 46 (36) : 6837 - 6839
  • [4] Rhodium-Catalyzed Asymmetric Conjugate Alkynylation of β,γ-Unsaturated α-Ketoesters
    Zhi, Yanle
    Huang, Jianhang
    Liu, Na
    Lu, Tao
    Dou, Xiaowei
    ORGANIC LETTERS, 2017, 19 (09) : 2378 - 2381
  • [5] Rhodium-Catalyzed Asymmetric Conjugate Alkynylation of Enones with Alkynylsilanols
    Nishimura, Takahiro
    Tokuji, Sumito
    Sawano, Takahiro
    Hayashi, Tamio
    ORGANIC LETTERS, 2009, 11 (15) : 3222 - 3225
  • [6] Rhodium-Catalyzed Asymmetric Conjugate Pyridylation with Pyridylboronic Acids
    Ye, Bihai
    Yao, Jian
    Wu, Changhui
    Zhu, Huilong
    Yao, Weijun
    Jin, Lili
    Dou, Xiaowei
    ACS CATALYSIS, 2022, 12 (04) : 2434 - 2440
  • [7] Rhodium-catalyzed intramolecular hydrosilylation of allenes
    Commandeur, C
    Varchi, G
    Shimizu, K
    Ojima, I
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2005, 230 : U3248 - U3249
  • [8] Rhodium-Catalyzed Hydrosilylation of Alkenes with Acylhydrosilanes
    Lind, Florian
    Studer, Armido
    CHEMISTRY-A EUROPEAN JOURNAL, 2023, 29 (40)
  • [9] Rhodium-catalyzed asymmetric conjugate addition of organoboronic acids to nitroalkenes
    Hayashi, T
    Senda, T
    Ogasawara, M
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (43) : 10716 - 10717
  • [10] Asymmetric Synthesis of β-Alkynyl Aldehydes by Rhodium-Catalyzed Conjugate Alkynylation
    Nishimura, Takahiro
    Sawano, Takahiro
    Hayashi, Tamio
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (43) : 8057 - 8059
12345