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通过手性伯胺催化实现试剂控制的β-酮羰基不对称氟化反应的对映选择性开关。

Reagent-controlled enantioselectivity switch for the asymmetric fluorination of β-ketocarbonyls by chiral primary amine catalysis.

作者信息

You Yang'en, Zhang Long, Luo Sanzhong

机构信息

Beijing National Laboratory for Molecule Sciences (BNLMS) , Key Laboratory for Molecular Recognition and Function , Institute of Chemistry , The Chinese Academy of Sciences , Beijing 100190 , China . Email:

University of Chinese Academy of Sciences , Beijing , 100049 , China.

出版信息

Chem Sci. 2017 Jan 1;8(1):621-626. doi: 10.1039/c6sc03109a. Epub 2016 Aug 26.

DOI:10.1039/c6sc03109a
PMID:28451209
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5358536/
Abstract

A reagent-controlled enantioselectivity switch was uncovered in the asymmetric α-fluorination of β-ketocarbonyls by a chiral primary amine catalyst. By a simple swap of fluorination reagents, both enantiomers of the quaternary fluorination adducts could be obtained with good yields and high enantioselectivity. Mechanistic studies disclosed dual H-bonding and electrostatic stereocontrolling modes for the catalysis.

摘要

在手性伯胺催化剂催化的β-酮羰基化合物的不对称α-氟化反应中，发现了一种试剂控制的对映选择性开关。通过简单地更换氟化试剂，可以以良好的产率和高对映选择性得到季铵化氟化加合物的两种对映体。机理研究揭示了催化过程中的双重氢键和静电立体控制模式。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fc9a/5358536/6a2774f6900b/c6sc03109a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fc9a/5358536/6cb6dac02037/c6sc03109a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fc9a/5358536/6a2774f6900b/c6sc03109a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fc9a/5358536/6cb6dac02037/c6sc03109a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fc9a/5358536/6a2774f6900b/c6sc03109a-f1.jpg

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