Highly Selective Intramolecular Carbene Insertion into Primary C-H Bond of α-Diazoacetamides Mediated by a (p-Cymene)ruthenium(II) Carboxylate Complex

被引：59
作者：
Lo, Vanessa Kar-Yan
Guo, Zhen
Choi, Matthew Kwok-Wai
Yu, Wing-Yiu
Huang, Jie-Sheng
Che, Chi-Ming [1 ]
机构：
[1] Univ Hong Kong, Inst Mol Technol Drug Discovery & Synth, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Hong Kong, Peoples R China
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 18期
关键词：
DIRHODIUM TETRACARBOXYLATE; COUPLING REACTIONS; MILD CONDITIONS; DIAZO COMPOUND; BETA-LACTAMS; FUNCTIONALIZATION; CATALYSTS; MECHANISM; LIGANDS;
D O I：
10.1021/ja3006989
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Complex [(p-cymene)Ru(eta(1)-O2CCF3)(2)(OH2)] mediated transformation of alpha-diazoacetamides ArCH2N(C(CH3)(3))C(O)CHN2 to result in carbene insertion into the primary C H bond exclusively, with the gamma-lactam products being isolated in up to 98% yield. This unexpected reaction is striking in view of the presence of usually more reactive sites such as secondary C-H bonds in the substrates. DFT calculations based on proposed Ru-carbene species provide insight into this unique selectivity.
引用
收藏
页码：7588 / 7591
页数：4
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共 43 条
  • [1] Half-sandwich ruthenium(II) complexes as catalysts for stereoselective carbene-carbene coupling reactions
    Baratta, W
    Del Zotto, A
    Rigo, P
    [J]. ORGANOMETALLICS, 1999, 18 (24) : 5091 - 5096
  • [2] Transition metal-catalyzed arylation of unactivated C(sp3)-H bonds
    Baudoin, Olivier
    [J]. CHEMICAL SOCIETY REVIEWS, 2011, 40 (10) : 4902 - 4911
  • [3] Selective functionalisation of saturated C-H bonds with metalloporphyrin catalysts
    Che, Chi-Ming
    Lo, Vanessa Kar-Yan
    Zhou, Cong-Ying
    Huang, Jie-Sheng
    [J]. CHEMICAL SOCIETY REVIEWS, 2011, 40 (04) : 1950 - 1975
  • [4] Thermal, catalytic, regiospecific functionalization of alkanes
    Chen, HY
    Schlecht, S
    Semple, TC
    Hartwig, JF
    [J]. SCIENCE, 2000, 287 (5460) : 1995 - 1997
  • [5] Palladium(II)-Catalyzed C-H Activation/C-C Cross-Coupling Reactions: Versatility and Practicality
    Chen, Xiao
    Engle, Keary M.
    Wang, Dong-Hui
    Yu, Jin-Quan
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (28) : 5094 - 5115
  • [6] Ruthenium porphyrin catalyzed intramolecular carbenoid C-H insertion. Stereloselective synthesis of cis-disubstituted oxygen and nitrogen heterocycles
    Cheung, WH
    Zheng, SL
    Yu, WY
    Zhou, GC
    Che, CM
    [J]. ORGANIC LETTERS, 2003, 5 (14) : 2535 - 2538
  • [7] A non-cross-linked soluble polystyrene-supported ruthenium catalyst for carbenoid transfer reactions
    Chi, Matthew Kwok-Wai
    Yu, Wing-Yiu
    So, Man-Ho
    Zhou, Cong-Ying
    Deng, Qing-Hai
    Che, Chi-Ming
    [J]. CHEMISTRY-AN ASIAN JOURNAL, 2008, 3 (8-9) : 1256 - 1265
  • [8] Ruthenium-catalyzed stereoselective intramolecular carbenoid C-H insertion for β- and γ-lactam formations by decomposition of α-diazoacetamides
    Choi, MKW
    Yu, WY
    Che, CM
    [J]. ORGANIC LETTERS, 2005, 7 (06) : 1081 - 1084
  • [9] INSERTION OF A VINYLIDENE UNIT INTO A RU-O BOND - SYNTHESIS AND MOLECULAR-STRUCTURE OF [C5H5(PPH3)RUC(=CHCO2ME)OC(ME)O]1
    DANIEL, T
    MAHR, N
    BRAUN, T
    WERNER, H
    [J]. ORGANOMETALLICS, 1993, 12 (04) : 1475 - 1477
  • [10] Catalytic enantioselective C-H activation by means of metal-carbenoid-induced C-H insertion
    Davies, HML
    Beckwith, REJ
    [J]. CHEMICAL REVIEWS, 2003, 103 (08) : 2861 - 2903
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