<p>Compounds containing all-carbon quaternary stereocenters are highly prominent in biological molecules and pharmaceuticals. The electrochemical enantioselective construction of such structural motifs offers an attractive approach for developing efficient and sustainable methodologies. Here, we demonstrate a nickel-catalyzed asymmetric diarylmethylation to construct quaternary carbon stereocenters via electrosynthesis. This reaction delivers highly enantioenriched <i>C</i><sup>α</sup>-tetrasubstituted <i>β</i>-keto esters with moderate to excellent yields. Mechanistic studies reveal that the addition of DIPEA not only serves as a base to faciliate <i>para</i>-quinone methides generation but also plays a crucial role in enantioselectivity control.</p>

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Nickel-catalyzed electrochemical asymmetric diarylmethylation for construction of quaternary carbon stereocenters

  • Wei-Feng Qian,
  • Yan-Yan Ouyang,
  • Tong Liu,
  • Ting Fang,
  • Zhi-Yong Fan,
  • Jin-Lin Zhang,
  • Cuiju Zhu,
  • Hao Xu

摘要

Compounds containing all-carbon quaternary stereocenters are highly prominent in biological molecules and pharmaceuticals. The electrochemical enantioselective construction of such structural motifs offers an attractive approach for developing efficient and sustainable methodologies. Here, we demonstrate a nickel-catalyzed asymmetric diarylmethylation to construct quaternary carbon stereocenters via electrosynthesis. This reaction delivers highly enantioenriched Cα-tetrasubstituted β-keto esters with moderate to excellent yields. Mechanistic studies reveal that the addition of DIPEA not only serves as a base to faciliate para-quinone methides generation but also plays a crucial role in enantioselectivity control.