N-heterocyclic carbene-catalyzed atroposelective synthesis of axially chiral 5-aryl 2-pyrones from enals  

作　　者：Guanjie Wang Juhui Huang Linxue Zhang Jinna Han Xiaoxiang Zhang Jie Huang Zhenqian Fu Wei Huang 

机构地区：[1]Key Laboratory of Flexible Electronics&Institute of Advanced Materials,Institute of Advanced Synthesis,School of Chemistry and Molecular Engineering,Nanjing Tech University,Nanjing 211816,China [2]Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources,College of Chemical Engineering,Nanjing Forestry University,Nanjing 210037,China [3]Ningbo Institute,Chongqing Technology innovation Center,Frontiers Science Center for Flexible Electronics(FSCFE),Northwestern Polytechnical University,Xi’an 710072,China

出　　处：《Science China Chemistry》2022年第10期1953-1961,共9页中国科学（化学英文版）

基　　金：supported by the National Key R&D Program of China (2017YFA0204704);the National Natural Science Foundation of China (21602105);the General Program of Chongqing Natural Science(cstc2020jcyj-msxmX0712);Ningbo Natural Science Foundation (202003N4063);the Natural Science Foundation of Jiangsu Province (BK20221309)

摘　　要：Axially chiral molecules have been widely used in inorganic,material and medicinal chemistry.Compared with well-established N-heterocyclic carbene(NHC)-catalyzed asymmetric construction of centrally chiral molecules,NHC-catalyzed atroposelective synthesis of axially chiral molecules remains largely underdeveloped.Notably,alkynyl acyl azolium intermediates were commonly used in constructing a heteroaryl ring to furnish axially enantioenriched heteroaryl-aryls.The inherent character of the intermediates often led to react with sterically hindered substrates difficultly.Herein,we have successfully disclosed the atroposelective synthesis of axially chiral heteroaryl-aryls from sterically hindered enols through the use of chiral NHCs as catalysts for highly enantioselective Coates-Claisen rearrangements via catalytically generatedα,β-unsaturated acyl azoliums.This approach will enable the concise synthesis of valuable tetra-ortho-substituted 2-pyrones in one step with good yield and chirality control.

关 键 词：N-heterocyclic carbene ORGANOCATALYSIS atroposelective synthesis 2-pyrones ENALS 

分 类 号：O626[理学—有机化学]