Rhodium-mediated intramolecular C-H insertion: Probing the geometry of the transition state

被引:41
|
作者
Taber, DF [1 ]
Malcolm, SC [1 ]
机构
[1] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA
来源
JOURNAL OF ORGANIC CHEMISTRY | 1998年 / 63卷 / 11期
关键词
D O I
10.1021/jo9803434
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The unsymmetrical alpha-diazo ester 1b, derived from the chiral naphthylborneol 5, was cyclized with a set of rhodium carboxylates (L = CF3CO2, CH3CO2, CH3(CH2)(6)CO2, (CH3)(3)CCO2). The ratio of the three major products ((R,R)-3b, (S,S)-3b, 4b) was determined. It was found that the rhodium catalyst derived from pivalic acid gave the highest ratio of 3b:4b. Lowering the temperature of the reaction (L = (CH3)(3)CCO2) increased both the yield and the diastereoselectivity of the cyclization. From these results and from our computational analysis, it is concluded that the ester carbonyl and the rhodium carbenoid are probably syn in the transition state leading to cyclization.
引用
收藏
页码:3717 / 3721
页数:5
相关论文
共 50 条
  • [21] Synthesis of bicyclic γ-butyrolactone derivatives by rhodium catalyzed intramolecular C-H insertion of α-dizao α-phosphoryl cycloalkyl esters
    Shie, Jr-Yun
    Zhu, Jia-Liang
    TETRAHEDRON, 2016, 72 (12) : 1590 - 1601
  • [22] Anomalous products from intramolecular C-H insertion by a rhodium carbenoid. Possible involvement of a zwitterionic mechanism
    White, JD
    Hrnciar, P
    JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (19): : 7271 - 7273
  • [23] Rhodium(II)-catalysed intramolecular C-H insertion α- to oxygen: reactivity, selectivity and applications to natural product synthesis
    Lombard, Fanny J.
    Coster, Mark J.
    ORGANIC & BIOMOLECULAR CHEMISTRY, 2015, 13 (23) : 6419 - 6431
  • [24] Intramolecular C-H insertion using NHC-di-rhodium(II) complexes: the influence of axial coordination
    Gomes, Luis F. R.
    Trindade, Alexandre F.
    Candeias, Nuno R.
    Gois, Pedro M. P.
    Afonso, Carlos A. M.
    TETRAHEDRON LETTERS, 2008, 49 (52) : 7372 - 7375
  • [25] Improved chemoselectivity in intramolecular alkylidene carbene C-H insertion
    Taber, DF
    Christos, TE
    TETRAHEDRON LETTERS, 1997, 38 (28) : 4927 - 4930
  • [26] Photoactivatable Fluorogens by Intramolecular C-H Insertion of Perfluoroaryl Azide
    Xie, Sheng
    Proietti, Giampiero
    Ramstrom, Olof
    Yan, Mingdi
    JOURNAL OF ORGANIC CHEMISTRY, 2019, 84 (22): : 14520 - 14528
  • [27] DIASTEREOSELECTIVITY IN UNCATALYZED INTRAMOLECULAR C-H INSERTION BY AN ALKYLIDENE CARBENE
    TABER, DF
    MEAGLEY, RP
    TETRAHEDRON LETTERS, 1994, 35 (43) : 7909 - 7910
  • [28] INTRAMOLECULAR C-H INSERTION IN ALKYLIDENE CARBENOIDS FOR CYCLOPENTENE DERIVATIVES
    FISCHER, RH
    BAUMANN, M
    KOBRICH, G
    TETRAHEDRON LETTERS, 1974, (13) : 1207 - 1208
  • [29] Transition Metal-Catalysed Intramolecular Carbenoid C-H Insertion for Pyrrolidine Formation by Decomposition of α-Diazoesters
    Sole, Daniel
    Amenta, Arianna
    Mariani, Francesco
    Bennasar, M. -Lluisa
    Fernandez, Israel
    ADVANCED SYNTHESIS & CATALYSIS, 2017, 359 (20) : 3654 - 3664
  • [30] Regioselectivity of Intramolecular Rhodium-Catalyzed C-H Insertion Reactions of α-Aryl-α-diazocarboxylates: Influence of the Aryl Substituent
    Wamser, Maximilian
    Bach, Thorsten
    SYNLETT, 2014, 25 (08) : 1081 - 1084