瑞典斯德哥尔摩大学
研究人员发现,内部有含氧或含氮亲核基团的1,1-二取代苯乙烯类化合物可以在原位生成的手性碘(III)催化剂存在下发生氧化氟环化反应。该反应生成的氟代四氢呋喃和吡咯烷类化合物含有一个手性叔碳中心C-F键。
进一步研究表明,用一种新的1-萘乳酸基碘(III)催化剂可使手性叔碳中心C-F键的ee值高达96%。研究人员还通过密度泛函理论计算来了解该反应的详细机理和主宰该反应手性选择性的因素。
附:英文原文
Title: Enantioselective Construction of Tertiary Fluoride Stereocenters by Organocatalytic Fluorocyclization
Author: Qiang Wang, Marvin Lübcke, Maria Biosca, Martin Hedberg, Lars Eriksson, Fahmi Himo, Kálmán J. Szabó
Issue&Volume: November 16, 2020
Abstract: 1,1-Disubstituted styrenes with internal oxygen and nitrogen nucleophiles undergo oxidative fluorocyclization reactions with in situ generated chiral iodine(III)-catalysts. The resulting fluorinated tetrahydrofurans and pyrrolidines contain a tertiary carbon–fluorine stereocenter. Application of a new 1-naphthyllactic acid-based iodine(III)-catalyst allows the control of tertiary carbon–fluorine stereocenters with up to 96% ee. Density functional theory calculations are performed to investigate the details of the mechanism and the factors governing the stereoselectivity of the reaction.
DOI: 10.1021/jacs.0c09323
Source: https://pubs.acs.org/doi/10.1021/jacs.0c09323
JACS:《美国化学会志》,创刊于1879年。隶属于美国化学会,最新IF:14.612
官方网址:https://pubs.acs.org/journal/jacsat
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