通过共轭加成/不对称质子化/氮杂-Prins串联反应合成对映体富集的二氢吲哚
Synthesis of Enantioenriched Indolines by a Conjugate Addition/Asymmetric Protonation/Aza-Prins Cascade Reaction.
作者信息
Daniels Blake E, Ni Jane, Reisman Sarah E
机构信息
The Warren and Katharine Schlinger Laboratory of Chemistry and Chemical Engineering, Division of Chemistry and ChemicalEngineering, California Institute of Technology, Pasadena, CA 91125, USA.
出版信息
Angew Chem Int Ed Engl. 2016 Mar 1;55(10):3398-402. doi: 10.1002/anie.201510972. Epub 2016 Feb 4.
Abstract
A conjugate addition/asymmetric protonation/aza-Prins cascade reaction has been developed for the enantioselective synthesis of fused polycyclic indolines. A catalyst system generated from ZrCl4 and 3,3'-dibromo-BINOL enables the synthesis of a range of polycyclic indolines in good yields and with high enantioselectivity. A key finding is the use of TMSCl and 2,6-dibromophenol as a stoichiometric source of HCl to facilitate catalyst turnover. This transformation is the first in which a ZrCl4 ⋅BINOL complex serves as a chiral Lewis-acid-assisted Brønsted acid.
摘要
已开发出一种共轭加成/不对称质子化/氮杂-Prins串联反应，用于对映选择性合成稠合多环吲哚啉。由ZrCl4和3,3'-二溴联萘酚生成的催化剂体系能够以良好的产率和高对映选择性合成一系列多环吲哚啉。一个关键发现是使用TMSCl和2,6-二溴苯酚作为HCl的化学计量来源以促进催化剂周转。这种转化是首次使用ZrCl4·联萘酚络合物作为手性路易斯酸辅助的布朗斯特酸。
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J Org Chem. 2015 Oct 16;80(20):9868-80. doi: 10.1021/acs.joc.5b01301. Epub 2015 Oct 2.
2
Bioinspired total synthesis of sespenine.仿生全合成 sespenine。
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3
Catalytic C-C bond-forming multi-component cascade or domino reactions: pushing the boundaries of complexity in asymmetric organocatalysis.催化碳-碳键形成的多组分串联或多米诺反应：拓展不对称有机催化的复杂性边界
Chem Rev. 2014 Feb 26;114(4):2390-431. doi: 10.1021/cr400215u. Epub 2013 Dec 4.
4
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