Intermolecular cyclopropanation versus CH insertion in RhII-catalyzed carbenoid reactions

被引：88
|
作者：
Müller, P [1 ]
Tohill, S [1 ]
机构：
[1] Univ Geneva, Dept Organ Chem, CH-1211 Geneva 4, Switzerland
来源：
TETRAHEDRON | 2000年 / 56卷 / 12期
关键词：
diazo decomposition; CH bond insertion; rhodium catalyst; asymmetric induction;
D O I：
10.1016/S0040-4020(00)00076-4
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The product ratio of intermolecular insertion and cyclopropanation in transition metal-catalyzed diazo decompositions depends strongly upon the metal, its ligands and upon the substituents of the diazo compound. Ethyl diazoacetate (2a) reacts with cyclohexene (1) almost exclusively by cyclopropanation. However, diazomalonate (2d) and methyl 2-diazophenylacetate (2e) in the presence of Rh-II catalysts exhibit a marked tendency towards allylic CH insertion. With 1,4-cyclohexadiene (6), methyl 2-diazophenylacetate (2e) in the presence of chiral Rh-II catalysts affords the allylic insertion product 7 in almost quantitative yield and with up to 74% ee. (C) 2000 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码：1725 / 1731
页数：7
相关论文
共 44 条
  • [1] RhII-catalyzed reactions of diazocarbonyl compounds with dicarboximides
    Nikolaev, Vsevolod V.
    Heimgartner, Heinz
    Linden, Anthony
    Krylov, Ivan S.
    Nikolaev, Valerij A.
    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2006, 2006 (20) : 4737 - 4746
  • [2] RhII-Catalyzed Intermolecular C-H Arylation of Aromatics with Diazo Quinones
    Wu, Kai
    Cao, Bei
    Zhou, Cong-Ying
    Che, Chi-Ming
    CHEMISTRY-A EUROPEAN JOURNAL, 2018, 24 (19) : 4815 - 4819
  • [3] Preparation and in situ use of unstable N-alkyl α-diazo-γ-butyrolactams in RhII-catalyzed X-H insertion reactions
    Eremeyeva, Maria
    Zhukovsky, Daniil
    Dar'in, Dmitrii
    Krasavin, Mikhail
    BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, 2020, 16 : 607 - 610
  • [4] Gold-catalyzed cyclopropanation reactions using a carbenoid precursor toolbox
    Qian, Deyun
    Zhang, Junliang
    CHEMICAL SOCIETY REVIEWS, 2015, 44 (03) : 677 - 698
  • [5] RhII-Catalyzed Reaction of α-Diazocarbonyl Compounds Bearing β-Trichloroacetylamino Substituent: C-H Insertion versus 1,2-H Shift
    Zhang, Zhenhua
    Shi, Weifeng
    Zhang, Jian
    Zhang, Bo
    Liu, Bingge
    Liu, Yiyang
    Fan, Bo
    Xiao, Fengping
    Xu, Feng
    Wang, Jianbo
    CHEMISTRY-AN ASIAN JOURNAL, 2010, 5 (05) : 1112 - 1119
  • [6] PALLADIUM CATALYZED INTERMOLECULAR CASCADE CYCLIZATION - CYCLOPROPANATION REACTIONS
    GRIGG, R
    SRIDHARAN, V
    TETRAHEDRON LETTERS, 1992, 33 (51) : 7965 - 7968
  • [7] Non-natural carbenoid and nitrenoid insertion reactions catalyzed by heme proteins
    Gober, Joshua G.
    Brustad, Eric M.
    CURRENT OPINION IN CHEMICAL BIOLOGY, 2016, 35 : 124 - 132
  • [8] (E)-3-Arylidene-4-diazopyrrolidine-2,5-diones: Preparation and Use in RhII-Catalyzed X-H Insertion Reactions towards Novel, Medicinally Important Michael Acceptors
    Chupakhin, Evgeny
    Gecht, Martha
    Ivanov, Alexander
    Kantin, Grigory
    Dar'in, Dmitry
    Krasavin, Mikhail
    SYNTHESIS-STUTTGART, 2021, 53 (07): : 1292 - 1300
  • [9] Semisynthesis of 3-Hydroxyoxindole Rapamycin Analogues Through Site- and Stereoselective Trapping of Oxonium Ylides in RhII-Catalyzed Three-Component Reactions
    Qiu, Lin
    Su, Meng
    Wen, Zhongqing
    Zhu, Xiangcheng
    Duan, Yanwen
    Huang, Yong
    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2019, 2019 (18) : 2914 - 2918
  • [10] Asymmetric intermolecular cyclopropanation of alkenes and N-H insertion of aminoesters by diazoacetylferrocene catalyzed by ruthenium and iron porphyrins
    Carrie, Daniel
    Roisnel, Thierry
    Simonneaux, Gerard
    POLYHEDRON, 2021, 205
12345