From Propargylic Fluorinations to [1,3]-Rearrangements: Anion and Ligand Effects in Cu-Acetylide Chemistry

Autor:	Christopher J. Cordier, Alexander P. N. Brown, Li-Jie Cheng
Rok vydání:	2018
Předmět:	010405 organic chemistry Chemistry Ligand Acetylide Organic Chemistry Reactive intermediate Enantioselective synthesis 010402 general chemistry 01 natural sciences Combinatorial chemistry 0104 chemical sciences Catalysis chemistry.chemical_compound Nucleophile Electrophile Bimetallic strip
Zdroj:	Synlett. 29:1675-1682
ISSN:	1437-2096 0936-5214
DOI:	10.1055/s-0036-1591997
Popis:	Metal-catalyzed reactions of propargylic substrates have been widely studied. Of this reaction class, Cu-catalyzed methods have received much attention within the past decade, with Cu-allenylidenes being proposed as key reactive intermediates. This Synpacts article will outline our development of a nucleophilic fluorination protocol of propargylic electrophiles using copper catalysis. Following an analysis of the importance of anion and ligand effects, this study led us to the unexpected discovery of a formal [1,3]-rearrangement of O-propargylic alkoxypyridine derivatives that was later rendered enantioselective. By contrast to Cu-allenylidene proposals, our mechanistic findings have identified alternatives involving bimetallic intermediates.1 Introduction2 Propargylic Fluorination3 Anion Effects4 Propargylic Rearrangements5 Mechanistic Studies6 Conclusions
Databáze:	OpenAIRE
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