GENERAL-ROUTE TO HIGHLY FUNCTIONALIZED CYCLOPENTANE DERIVATIVES BY INTRAMOLECULAR C-H INSERTION
GENERAL-ROUTE TO HIGHLY FUNCTIONALIZED CYCLOPENTANE DERIVATIVES BY INTRAMOLECULAR C-H INSERTION
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DOI：
10.1021/jo00145a050
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发表时间：
1982-01-01
影响因子：
3.6
通讯作者：
PETTY, EH
中科院分区：
文献类型：
--
作者：
TABER, DF;PETTY, EH
在重氮酮分子内插入CH的文献中有各种各样的例子。2在许多情况下，重氮部分被限制为与插入发生的CH键非常接近。我们已经发现，即使在非循环的自由旋转体系中，CH插入也可以是一个有效的过程。我们选择研究-重氮/3-酮酸酯的环化反应，因为它们很容易制备，通过Weiler3.456后重氮转移，5，6的方法制备，并且因为得到的β-酮酯将是进一步精制的多种中间体。(1)对应的环化反应应寄给作者，地址为：特拉华大学化学系，纽瓦克，DE 19711。(2)(A)有关重氮羰基化合物分子内反应的最新综述，见：Burke，S.D.；Grieco，P.A.Org。做出反应。(B)关于分子内CH插入的早期研究，见：LeDon，H.；LIntoelle，G.；Julia，S.Bull。SoC。化学。佛尔(C)关于金属催化的卡宾反应的详细分析，见：Wulfman，D.S.；Poling，B.“反应中间体”；Abramovitch，RA，Ed.；Plenum：New York，1980；Vol.1。(3)对应于5的酮酯是从柠檬醛制备的。甲基锂加成后经PCC氧化得到烯酮。暴露在Me2CuLi中导致甲基酮饱和，甲基酮在四氢呋喃中回流时用NaH和碳酸二甲酯进行甲氧基化。我们感谢萨米尔·萨利赫先生进行这项筹备工作。
There are a variety of examples in the literature of intramolecular CH insertion by diazo ketones. 2 In many of these cases, the diazo moiety was constrained to be quite close to the CH bond into which insertion took place. We have found that CH insertion can be an efficient process even in an acyclic, freely rotating system. We chose to investigate the cyclization of-diazo/3-keto esters because they are readily prepared, by the method of Weiler3· 4 56followed by diazo transfer, 5, 6 and because the resultant ß-ketoesters would be versatile intermediates for further elaboration. The cyclizations that have been (1) Correspondence should be addressed to this author at the De-partment of Chemistry, University of Delaware, Newark, DE 19711.(2)(a) For a recent review of intramolecular reactions of diazocarbonyl compounds, see: Burke, S. D.; Grieco, P. A. Org. React. 1979, 26, 361.(b) For an early study of intramolecular CH insertion, see: Ledon, H.; Linstrumelle, G.; Julia, S. Bull. Soc. Chem. Fr. 1973, 2071.(c) For a detailed analysis of metal-catalyzed carbenoid reactions, see: Wulfman, D. S.; Poling, B.“Reactive Intermediates”; Abramovitch, RA, Ed.; Plenum: New York, 1980; Vol. 1.(3) The keto ester corresponding to 5 was prepared from citral. Ad-dition of methyl lithium followed by PCC oxidation gave the enone. Exposure to Me2CuLi led to the saturated methyl ketone, which was carbomethoxylated by treatment with NaH and dimethyl carbonate in THF at reflux. We thank Mr. Samir A. Saleh for carrying out this preparation.