A comparative study of the solvolysis reactivity, regioselectivity, and stereochemistry of the duocarmycin A and SA alkylation subunits
A comparative study of the solvolysis reactivity, regioselectivity, and stereochemistry of the duocarmycin A and SA alkylation subunits
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DOI：
10.1016/0960-894x(96)00346-0
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发表时间：
1996-08-20
影响因子：
2.7
通讯作者：
McKie, JA
中科院分区：
文献类型：
--
作者：
Boger, DL;Goldberg, J;McKie, JA
详细介绍了 N-BOC-DSA (4) 和 N-BOC-DA (5)（duocarmycin SA 和 A 的 DNA 烷基化亚基的简单衍生物）的比较溶剂解反应性、区域选择性和立体化学。最重要的观察结果是 5 相对于 4 (16x) 具有更高的反应性，4 (6.5-4:1) 和 5 (1.5:1) 均具有适度的区域选择性，以及通过将 S(N)2 添加到活化的环丙烷中进行异常扩环溶剂分解，并彻底反转反应中心立体化学。版权所有 (C) 1996 爱思唯尔科学有限公司
The comparative solvolysis reactivity, regioselectivity, and stereochemistry of N-BOC-DSA (4) and N-BOC-DA (5), simple derivatives of the DNA alkylation subunits of duocarmycin SA and A, are detailed. Most important of the observations is the substantially greater reactivity of 5 versus 4 (16x), the modest regioselectivity of both 4 (6.5-4:1) and 5 (1.5:1), and the establishment that the abnormal ring expansion solvolysis proceeds by S(N)2 addition to the activated cyclopropane with clean inversion of the reacting center stereochemistry. Copyright (C) 1996 Elsevier Science Ltd