Rémi Blieck1, Marc Taillefer1, Florian Monnier1,2. 1. Institut Charles Gerhardt Montpellier UMR 5253, Université Montpellier, CNRS, ENSCM, 8 rue de l'Ecole Normale, Montpellier 34296, Cedex 5, France. 2. Institut Universitaire de France, IUF, 1 rue Descartes, 75231 Paris, cedex 5, France.
Abstract
Following a strong regain of interest over the past 20 years in the chemistry of allenes, this "forgotten" family of unsaturated molecules is undergoing a renaissance. In this context, the metal-catalyzed hydrofunctionalization of allenes is nowadays one of the most studied transformations. The latter is of great interest because it opens a way to produce selectively functionalized allylic structures. These motifs are important in synthesis, particularly for the formation of asymmetric centers. Hydrofunctionalization of allenes is also a totally atom economical strategy, avoiding generation of any waste, to produce allylic functionalized structures. Compared to the main pathway to obtain the latter (aka Tsuji-Trost allylic substitution), metal-catalyzed hydrofunctionalization does not require the prefunctionalization of starting material with a leaving group. This review presents a state of the art exploration of all existing transition metal-catalyzed methods allowing the selective intermolecular hydrofunctionalization of allenes with N-H, C-H, and O-H nucleophiles or electrophiles.
Following a strong regain of interest over the past 20 years in the chemistry of allenes, this "forgotten" family of unsaturated molecules is undergoing a renaissance. In this context, the n class="Chemical">metal-catalyzed hydrofunctionalization of allenes is nowadays one of the most studied transformations. The latter is of great interest because it opens a way to produce selectively functionalized allylic structures. These motifs are important in synthesis, particularly for the formation of asymmetric centers. Hydrofunctionalization of allenes is also a totally atom economical strategy, avoiding generation of any waste, to produce allylic functionalized structures. Compared to the main pathway to obtain the latter (aka Tsuji-Trost allylic substitution), metal-catalyzed hydrofunctionalization does not require the prefunctionalization of starting material with a leaving group. This review presents a state of the art exploration of all existing transition metal-catalyzed methods allowing the selective intermolecular hydrofunctionalization of allenes with N-H, C-H, and O-H nucleophiles or electrophiles.
Authors: Yidong Wang; Sarah G Scrivener; Xiao-Dong Zuo; Ruihan Wang; Philip N Palermo; Ethan Murphy; Austin C Durham; Yi-Ming Wang Journal: J Am Chem Soc Date: 2021-09-07 Impact factor: 16.383