Heteroatom-Directed Acylation of Secondary Alcohols To Assign Absolute Configuration
Heteroatom-Directed Acylation of Secondary Alcohols To Assign Absolute Configuration
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DOI：
10.1021/acs.joc.7b03156
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发表时间：
2018-03-02
影响因子：
3.6
通讯作者：
Rychnovsky, Scott D.
中科院分区：
文献类型：
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作者：
Burns, Alexander S.;Ross, Christopher C.;Rychnovsky, Scott D.
Birman的HBTM催化剂对苯仲醇的对映选择性酰化反应和动力学拆分反应是有效的。对映选择性酰化现在已扩展到具有吸电子基团的仲醇，如卤化物和其他杂原子。选择性水平从中等到良好，足以使用竞争性对映选择性转换方法确定配置。数学分析确定了实现最大转换差异的条件，从而更有信心地分配配置。新方法对卤代醇和1,2-叔二醇的反应是有效的，并用于确定两种萜类天然产物的构型。
Birman's HBTM catalyst is effective for the enantioselective acylation and kinetic resolution of benzylic secondary alcohols. The enantioselective acylation has now been extended to secondary alcohols bearing electron withdrawing groups such as halides and other heteroatoms. The level of selectivity is modest to good and is sufficient for determining configuration using the competing enantioselective conversion method. A mathematical analysis identifies conditions for achieving maximum differences in conversion and, consequently, assigning configuration with greater confidence. The new method is effective for halohydrins and secondary-tertiary 1,2-diols and was used to confirm the configuration of two inoterpene natural products.