Fluoro-Analoga of Cycloheptadiene Pheromones of Marine Brown-Algae - Exceptionally Facile [3,3]-Sigmatropic Rearrangement of a Trans-Di(Alkenyl)-Substituted Geminal Difluorocyclopropane
Fluoro-Analoga of Cycloheptadiene Pheromones of Marine Brown-Algae - Exceptionally Facile [3,3]-Sigmatropic Rearrangement of a Trans-Di(Alkenyl)-Substituted Geminal Difluorocyclopropane
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海洋褐藻环庚二烯信息素的氟类似物 - 反式二（烯基）取代的双二氟环丙烷的极其容易的 [3,3]-Sigmatropic 重排
DOI：
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发表时间：
1992
期刊：
影响因子：
--
通讯作者：
W. Boland
中科院分区：
文献类型：
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作者：
P. Erbes;W. Boland
褐藻环庚烯类信息素的氟类似物：反式-二（烯基）-取代的偕二氟环丙烷的[3，3]-σ迁移重排
3，3-二氟环丙烷-1，2-二羰基化合物9a和9 b是通过将二氟卡宾加成到肉桂酸甲酯或反式二苯乙烯上，然后氧化降解苯环而获得的（方案2）。化合物9 b是用于合成二（烯基）取代的偕二氟环丙烷5或菊酯10 b的通用结构单元。环丙烷5在室温下不稳定，并重排为3，3-二氟环庚-1，4-二烯4，其为藻类信息素网烯的类似物（1;方案3）。测定了[3，3]-σ迁移重排反应的动力学参数。这些数据支持环丙烷内的偕二氟基团削弱远端键的观点。
Fluoro Analoga of Cycloheptadiene Pheromones of Marine Brown Algae: Exceptionally Facile [3,3]-Sigmatropic Rearrangement of a trans-Di(alkenyl)-Substituted Geminal Difluorocyclopropane
The 3,3,-difluorocyclopropane-1,2-dicarbonyl compounds 9a and 9b are obtained by addition of difluorocarbene to methyl cinnamate or trans-stilbene followed by oxidative degradation of the phenyl rings(s) (Scheme 2). Compound 9b is a versatile building block for the synthesis of the di(alkenyl)-substituted geminal difluorocyclopropane 5 or the chrysanthemum ester 10b. Cyclopropane 5 is unstable at room temperature and rearranges to the 3,3,-difluorocyclohepta-1,4-diene 4, an analog of the algal pheromone dictyotene (1; Scheme 3). The kinetic parameters of the [3,3]-sigmatropic rearrangement are determined. The data support the view that a geminal difluoro group within a cyclopropane weakens the distal bond.
DOI：
10.1073/pnas.82.24.8827
发表时间：
1985-12
影响因子：
11.1
作者：
Richard G. Vogt;L. Riddiford;Glenn D. Prestwich
通讯作者：
Richard G. Vogt;L. Riddiford;Glenn D. Prestwich