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阴离子抽取催化：双氢键供体对α-氯醚活化的协同机制

Anion-Abstraction Catalysis: The Cooperative Mechanism of α-Chloroether Activation by Dual Hydrogen-Bond Donors.

作者信息

Ford David D, Lehnherr Dan, Kennedy C Rose, Jacobsen Eric N

机构信息

Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.

出版信息

ACS Catal. 2016 Jul 1;6(7):4616-4620. doi: 10.1021/acscatal.6b01384. Epub 2016 Jun 10.

DOI:10.1021/acscatal.6b01384
PMID:31754547
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6870875/
Abstract

We provide here a detailed mechanistic characterization of the electrophile-activation step in a representative thiourea-catalyzed enantioselective reaction proposed to involve generation of ion-pair intermediates. Comparison of catalyst-promoted substrate epimerization with catalytic alkylation points to the participation of a common intermediate in both pathways and provides conclusive evidence for anion abstraction via an SN1-like pathway involving the cooperative action of two catalyst molecules.

摘要

我们在此提供了对一种代表性的硫脲催化对映选择性反应中亲电试剂活化步骤的详细机理表征，该反应被认为涉及离子对中间体的生成。将催化剂促进的底物差向异构化与催化烷基化进行比较，表明两种途径中存在共同中间体，并为通过涉及两个催化剂分子协同作用的类SN1途径进行阴离子提取提供了确凿证据。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3137/6870875/258f8e1b4dfa/nihms-1013239-f0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3137/6870875/568bf8caae67/nihms-1013239-f0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3137/6870875/b21f88bb2493/nihms-1013239-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3137/6870875/c35a0d9b3657/nihms-1013239-f0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3137/6870875/99f4695153ca/nihms-1013239-f0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3137/6870875/258f8e1b4dfa/nihms-1013239-f0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3137/6870875/568bf8caae67/nihms-1013239-f0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3137/6870875/b21f88bb2493/nihms-1013239-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3137/6870875/c35a0d9b3657/nihms-1013239-f0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3137/6870875/99f4695153ca/nihms-1013239-f0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3137/6870875/258f8e1b4dfa/nihms-1013239-f0006.jpg

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