Hydroxymethylation beyond Carbonylation: Enantioselective Iridium-Catalyzed Reductive Coupling of Formaldehyde with Allylic Acetates via Enantiotopic π-Facial Discrimination.
Hydroxymethylation beyond Carbonylation: Enantioselective Iridium-Catalyzed Reductive Coupling of Formaldehyde with Allylic Acetates via Enantiotopic π-Facial Discrimination.
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DOI：
10.1021/jacs.6b01078
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发表时间：
2016-03-23
影响因子：
15
通讯作者：
Krische MJ
中科院分区：
文献类型：
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作者：
Garza VJ;Krische MJ
经SEGPHOS修饰的手性Ir络合物催化2-丙醇催化支链烯丙基乙酸酯1a-1o与甲醛还原偶联生成伯烯丙醇2a-2o，具有良好的区域选择性和对映体选择性。这些过程依赖于对映体π-σ-烯丙基锂中间体的面部识别，是第一个超越Aldol加成的对映体选择性甲醛C-C偶联的例子。
Chiral iridium complexes modified by SEGPHOS catalyze the 2-propanol mediated reductive coupling of branched allylic acetates 1a–1o with formaldehyde to form primary homoallylic alcohols 2a–2o with excellent control of regio- and enantioselectivity. These processes, which rely on enantiotopic π-facial discrimination of σ-allyliridium intermediates, represent the first examples of enantioselective formaldehyde C-C coupling beyond aldol addition.