<p>Introducing saturated carbon-carbon bonds into organic molecules significantly increases the three-dimensional configuration, thus altering the physical and chemical properties as well as the functions of molecules. Transition-metal-catalyzed carbon-carbon cross-couplings represent one of the most straightforward, efficient and modular alternatives to build saturation in a single step. However, the efficient construction of alkyl-alkyl bonds remains a formidable challenge due to the precise manipulation of multiple alkyl metallic intermediates as well as associated competitive side reactions and selectivity control. Over the past years, Ni-catalyzed cross-coupling under reductive conditions has gained more and more attention for alkyl-alkyl cross-coupling partially attributing to the low-valent state of metal centers under reducing conditions, which suppresses the competitive β-hydride elimination process, thus facilitating the formation of alkyl-alkyl bonds. In this review, the initiative and progress of Ni-catalyzed cross-electrophile alkyl-alkyl cross-coupling, including the efforts in racemic and enantioselective formation of alkyl-alkyl bonds, have been summarized and discussed. Moreover, the challenges and further opportunities in this area have also been discussed.</p>

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Ni-catalyzed cross-electrophile alkyl-alkyl coupling reactions

  • Li-Xu You,
  • Lan Tian,
  • Chun-Ling Guo,
  • Shun-Xi Li,
  • Yu-Cheng Liu,
  • Yu-Long Li,
  • Wei Shu

摘要

Introducing saturated carbon-carbon bonds into organic molecules significantly increases the three-dimensional configuration, thus altering the physical and chemical properties as well as the functions of molecules. Transition-metal-catalyzed carbon-carbon cross-couplings represent one of the most straightforward, efficient and modular alternatives to build saturation in a single step. However, the efficient construction of alkyl-alkyl bonds remains a formidable challenge due to the precise manipulation of multiple alkyl metallic intermediates as well as associated competitive side reactions and selectivity control. Over the past years, Ni-catalyzed cross-coupling under reductive conditions has gained more and more attention for alkyl-alkyl cross-coupling partially attributing to the low-valent state of metal centers under reducing conditions, which suppresses the competitive β-hydride elimination process, thus facilitating the formation of alkyl-alkyl bonds. In this review, the initiative and progress of Ni-catalyzed cross-electrophile alkyl-alkyl cross-coupling, including the efforts in racemic and enantioselective formation of alkyl-alkyl bonds, have been summarized and discussed. Moreover, the challenges and further opportunities in this area have also been discussed.