Nickel(II)-Catalyzed Asymmetric Propargyl [2,3]Wittig Rearrangement of Oxindole Derivatives:A Chiral Amplification Effect
Nickel(II)-Catalyzed Asymmetric Propargyl [2,3]Wittig Rearrangement of Oxindole Derivatives:A Chiral Amplification Effect
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镍(II)催化羟吲哚衍生物的不对称炔丙基[2,3]Wittig重排：手性放大效应
DOI：
10.1002/anie.201804080
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Xiaoming Feng
中科院分区：
文献类型：
--
作者：
Xi Xu;Jianlin Zhang;Shunxi Dong;Lili Lin;Xiaobin Lin;Xiaohua Liu;Xiaoming Feng
以手性N，N′-dioxide/Ni Ⅱ配合物为催化剂，在温和的反应条件下，实现了羟吲哚衍生物的[2，3]Wittig重排反应.该催化剂具有很强的手性放大效应，通过使用ee值仅为15%的配体，可以高产率、高对映选择性地合成带有联烯基的手性3-羟基3-取代羟吲哚（ee值高达92%），并结合对映异构体纯催化剂和外消旋催化剂的X-射线晶体结构给出了合理的解释.首次实现了外消旋吲哚酮衍生物的[2，3] Wittig重排催化动力学拆分，拆分效率高，立体选择性好。
A highly enantioselective [2,3] Wittig rearrangement of oxindole derivatives was realized by using a chiralN,N′‐dioxide/NiIIcomplex as the catalyst under mild reaction conditions. A strong chiral amplification effect was observed, and allowed access to chiral 3‐hydroxy 3‐substituted oxindoles bearing allenyl groups in high yields and enantioselectivities (up to 92 %ee) by using a ligand with only 15 %ee. A reasonable explanation was given based on the experimental investigations and X‐ray crystal structures of enantiomerically pure and racemic catalysts. Moreover, the first catalytic kinetic resolution of racemic oxindole derivatives by a [2,3] Wittig rearrangement was realized with high efficiency and stereoselectivity.