恶唑啉作为双功能无痕发色团和手性助剂：多杂环酮的对映选择性光辅助合成
Oxazolines as Dual-Function Traceless Chromophores and Chiral Auxiliaries: Enantioselective Photoassisted Synthesis of Polyheterocyclic Ketones.
作者信息
Mukhina Olga A, Kutateladze Andrei G
机构信息
Department of Chemistry and Biochemistry, University of Denver , Denver, Colorado 80208-2436, United States.
出版信息
J Am Chem Soc. 2016 Feb 24;138(7):2110-3. doi: 10.1021/jacs.5b12690. Epub 2016 Feb 16.
Abstract
2-(o-Amidophenyl)oxa- and -thiazolines undergo excited-state intramolecular proton transfer (ESIPT), generating aza-o-xylylenes capable of intramolecular [4+2] and [4+4] cycloadditions with tethered unsaturated pendants. Facile hydrolysis of the primary photoproducts, spiro-oxazolidines and thiazolidines, under mild conditions unmasks a phenone functionality. Variations in linkers allow for access to diverse core scaffolds in the primary photoproducts, rendering the approach compatible with the philosophy of diversity-oriented synthesis. Chiral oxazolines, readily available from the corresponding amino alcohols, yield enantioenriched keto-polyheterocycles of complex topologies with enantiomeric excess values up to 90%.
摘要
2-(邻氨基苯基)恶唑啉和噻唑啉经历激发态分子内质子转移(ESIPT)，生成能够与连接的不饱和侧链进行分子内[4+2]和[4+4]环加成反应的氮杂邻亚二甲苯基。在温和条件下，初级光产物螺恶唑烷和噻唑烷的容易水解揭示了苯甲酮官能团。连接基的变化允许获得初级光产物中的各种核心支架，使得该方法与多样化导向合成的理念兼容。手性恶唑啉很容易从相应的氨基醇获得，产生对映体过量值高达90%的具有复杂拓扑结构的对映体富集的酮-多杂环。
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