From Propargylic Fluorinations to [1,3]-Rearrangements: Anion and Ligand Effects in Cu-Acetylide Chemistry
From Propargylic Fluorinations to [1,3]-Rearrangements: Anion and Ligand Effects in Cu-Acetylide Chemistry
复制标题
从丙炔氟化到 [1,3]-重排：铜乙酰化物化学中的阴离子和配体效应
作者：
Cordier C
金属催化丙炔底物的反应得到了广泛的研究。在这类反应中，cu催化的方法在过去的十年中受到了广泛的关注，其中cu -烯丙二烯被认为是关键的反应中间体。这篇Synpacts文章将概述我们使用铜催化丙炔亲电试剂的亲核氟化方案的发展。在分析了阴离子和配体效应的重要性之后，这项研究使我们意外地发现了o -丙基烷氧基吡啶衍生物的形式[1,3]重排，该衍生物后来具有对映选择性。与cu - allenlidee提案相比，我们的机制发现已经确定了涉及双金属中间体的替代品前言2丙炔氟化3阴离子效应4丙炔重排5机理研究6结论
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 ofO-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
影响因子：
5.4
作者：
Ardolino, Michael J.;Eno, Meredith S.;Morken, James P.
通讯作者：
Morken, James P.