Asymmetric Tandem 1,5-Hydride Shift/Ring Closure for the Synthesis of Chiral Spirooxindole Tetrahydroquinolines
Asymmetric Tandem 1,5-Hydride Shift/Ring Closure for the Synthesis of Chiral Spirooxindole Tetrahydroquinolines
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不对称串联 1,5-氢化物移位/闭环用于合成手性螺吲哚四氢喹啉
DOI：
10.1002/chem.201404327
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发表时间：
2015-01-19
影响因子：
4.3
通讯作者：
Feng, Xiaoming
中科院分区：
文献类型：
--
作者：
Cao, Weidi;Liu, Xiaohua;Feng, Xiaoming
本文描述了通过串联的1，5-氢化物移位/环闭合来直接官能化sp(3)C-H键。各种具有光学活性的螺氧吲哚四氢喹啉衍生物很容易合成，这些衍生物含有连续的四元或三元立体碳中心。N，N‘-二氧化Sc手性络合物以良好的非对映选择性(>；20：1)和对映体选择性(高达94%ee)促进了反应的进行。进行了手性底物的动力学同位素效应(KIE)实验和内部氧化还原反应，结果提供了有趣的信息，有助于阐明反应机理。
The direct functionalization of sp(3) C-H bonds through a tandem 1,5-hydride shift/ring closure is described. Various optically active spirooxindole tetrahydroquinoline derivatives bearing contiguous quaternary or tertiary stereogenic carbon centers were readily synthesized. A chiral scandium complex of N,N'-dioxide promoted the reactions in good yields (up to 97%) with excellent diastereoselectivities (>20:1) and enantioselectivities (up to 94% ee). Kinetic isotope effect (KIE) experiments and internal redox reactions of chiral substrates were conducted, and the results provided intriguing information that helped clarify the mechanism of the reaction.