Cationic Cyclizations Involving Olefinic Bonds. II.1 Solvolysis of 5-Hexenyl and trans-5,9-Decadienyl p-Nitrobenzenesulfonates
Cationic Cyclizations Involving Olefinic Bonds. II.1 Solvolysis of 5-Hexenyl and trans-5,9-Decadienyl p-Nitrobenzenesulfonates
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涉及烯键的阳离子环化。
DOI：
10.1021/ja01064a012
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发表时间：
1964
影响因子：
15
通讯作者：
J. Crandall
中科院分区：
文献类型：
--
作者：
W. S. Johnson;D. M. Bailey;R. Owyang;R. Bell;B. Jaques;J. Crandall
5-己烯基-硝基苯磺酸盐在含有甲酸钠的98%甲酸中溶解时，烯烃键的参与速度大约是己基酯的两倍。皂化后的产物由68%的环己醇、26%的己醇、5%的环己烯和1%的其他碳氢化合物组成。4-戊烯醇和6-庚烯醇的硝基苯磺酸盐的反应以负双键参与进行，主要是直接取代产物。反式- 5,9 -十二烯基/>-硝基苯磺酸酯的生成速率加快，并以单环产物为主。制备了一些双环材料，这些材料被证明是铁-十氢化萘衍生物。未发现顺式十萘化合物。与类环异戊二烯的生物合成有关的是伊朗融合双环材料的独特形成。二烯和多烯的酸催化环化通常缺乏选择性，因为阳离子位点不加选择地产生。我们把注意力集中在这样的系统上，在这种系统中，这种位点可以在特定位置产生，并且在酸性不足以产生重大竞争的条件下产生
Solvolysis of 5-hexenyl^-nitrobenzenesulfonate in 98% formic acid containing sodium formate proceeds with participation of the olefinic bond at a rate which is about twice that of the formolysis of the hexyl ester. The product, after saponification, consisted of 68% cyclohexanol, 26% hexenol, 5% cyclohexene, and 1% other hydrocarbons. Formolysis of the^-nitrobenzenesulfonates of 4-pentenol and 6-heptenol proceeded with neg-ligible double bond participation to give mainly the products of direct substitution. Formolysis of trans-5, 9-decadienyl/>-nitrobenzenesulfonate proceeded with rate acceleration and afforded mainly monocyclic products. Some bicyclic materials were produced and these were shown to be iroMS-decalin derivatives. No cis-decalin compounds were found. The exclusive formation of irans-fused bicyclic materials is of interest in connection with the biosynthesis of cycloisoprenoids.The acid-catalyzedcyclization of dienes and polyenes generally lacks selectivity because of the indiscriminate generation of cationic sites. We are directing our at-tention to systems in which such sites can be generated at a specific position and under conditions which are not acidic enough to effect significant competing