Silva Thiago S, Coelho Fernando
Laboratory of Synthesis of Natural Products and Drugs, Department of Organic Chemistry, Chemistry Institute, University of Campinas, PO Box 6154 - 13083-970, Campinas - SP, Brazil.
Beilstein J Org Chem. 2021 Jul 7;17:1565-1590. doi: 10.3762/bjoc.17.112. eCollection 2021.
Olefin double-bond functionalization has been established as an excellent strategy for the construction of elaborate molecules. In particular, the hydroalkylation of olefins represents a straightforward strategy for the synthesis of new C(sp)-C(sp) bonds, with concomitant formation of challenging quaternary carbon centers. In the last 20 years, numerous hydroalkylation methodologies have emerged that have explored the diverse reactivity patterns of the olefin double bond. This review presents examples of olefins acting as electrophilic partners when coordinated with electrophilic transition-metal complexes or, in more recent approaches, when used as precursors of nucleophilic radical species in metal hydride hydrogen atom transfer reactions. This unique reactivity, combined with the wide availability of olefins as starting materials and the success reported in the construction of all-carbon C(sp) quaternary centers, makes hydroalkylation reactions an ideal platform for the synthesis of molecules with increased molecular complexity.
烯烃双键官能团化已成为构建复杂分子的一种出色策略。特别是，烯烃的氢烷基化代表了一种直接合成新的C(sp³)-C(sp³)键的策略，同时还会形成具有挑战性的季碳中心。在过去20年中，出现了许多氢烷基化方法，这些方法探索了烯烃双键的多种反应模式。本综述展示了烯烃在与亲电过渡金属配合物配位时作为亲电伙伴的例子，或者在最近的方法中，在金属氢化物氢原子转移反应中用作亲核自由基物种前体时的例子。这种独特的反应性，再加上烯烃作为起始原料的广泛可得性以及在全碳C(sp³)季碳中心构建中所报道的成功，使得氢烷基化反应成为合成分子复杂性增加的分子的理想平台。
