Institut Charles Gerhardt Montpellier UMR 5253, Université Montpellier, CNRS, ENSCM, 8 rue de l'Ecole Normale, Montpellier 34296, Cedex 5, France.
Institut Universitaire de France, IUF, 1 rue Descartes, 75231 Paris, cedex 5, France.
Chem Rev. 2020 Dec 23;120(24):13545-13598. doi: 10.1021/acs.chemrev.0c00803. Epub 2020 Dec 10.
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.
在过去的 20 年中，人们对烯丙基的化学性质产生了浓厚的兴趣，这个“被遗忘”的不饱和分子家族正在经历复兴。在这种情况下，烯丙基的金属催化氢官能化反应是目前研究最多的转化反应之一。后者之所以受到广泛关注，是因为它为选择性合成官能化烯丙基结构提供了一种途径。这些结构在合成中非常重要，特别是在形成不对称中心方面。烯丙基的氢官能化反应也是一种完全原子经济性的策略，避免了任何废物的产生，从而生成了官能化的烯丙基结构。与获得后者的主要途径（即 Tsuji-Trost 烯丙基取代反应）相比，金属催化的氢官能化反应不需要将起始原料预先官能化形成离去基团。本文综述了目前所有过渡金属催化方法的研究进展，这些方法允许与 N-H、C-H 和 O-H 亲核试剂或亲电试剂选择性地进行烯丙基的分子间氢官能化反应。
