1,2-氮杂硼烷的硼保护基策略。
A Boron Protecting Group Strategy for 1,2-Azaborines.
机构信息
Department of Chemistry, Boston College , Chestnut Hill, Massachusetts 02467-3860, United States.
出版信息
J Am Chem Soc. 2017 Oct 25;139(42):15259-15264. doi: 10.1021/jacs.7b09491. Epub 2017 Oct 11.
Abstract
Upon reaction with either molecular oxygen or di-tert-butylperoxide in the presence of a simple copper(I) salt and an alcohol, a range of 1,2-azaborines readily exchange B-alkyl or B-aryl moieties for B-alkoxide fragments. This transformation allows alkyl and aryl groups to serve for the first time as removable protecting groups for the boron position of 1,2-azaborines during reactions that are not compatible with the easily modifiable B-alkoxide moiety. This reaction can be applied to synthesize a previously inaccessible BN isostere of ethylbenzene, a compound of interest in biomedical research. A sequence of epoxide ring opening using N-deprotonated 1,2-azaborines followed by an intramolecular version of the boron deprotection reaction can be applied to access the first examples of BN isosteres of dihydrobenzofurans and benzofurans, classes of compounds that are important to medicinal chemistry and natural product synthesis.
摘要
在简单的一价铜盐和醇的存在下，与分子氧或二叔丁基过氧化物反应时，一系列 1,2-氮杂硼烷很容易将 B-烷基或 B-芳基取代基交换为 B-烷氧基片段。这种转化允许烷基和芳基基团首次作为 1,2-氮杂硼烷硼原子的可去除保护基团，用于与易于修饰的 B-烷氧基取代基不兼容的反应中。该反应可用于合成以前无法获得的 BN 等排体乙基苯，这是生物医学研究中感兴趣的化合物。使用去质子化的 1,2-氮杂硼烷进行环氧化物开环的序列，然后进行硼脱保护反应的分子内版本，可以用于获得二氢苯并呋喃和苯并呋喃的 BN 等排体的第一个实例，这些化合物类对于药物化学和天然产物合成非常重要。
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