Department of Chemistry and Chemical Biology, Stevens Institute of Technology, Hoboken, New Jersey 07030, United States.
J Org Chem. 2022 Aug 5;87(15):9896-9906. doi: 10.1021/acs.joc.2c00914. Epub 2022 Jul 12.
Conjugate addition of α-boron-stabilized carbanions is an underexplored reaction modality. Existing methods require deborylation of geminal di-/triboryl alkanes and/or the presence of additional activating groups. We report the 1,4-addition of α,α-diboryl carbanions generated via deprotonation of the corresponding geminal diborons. The methodology provided a general route to highly substituted and synthetically useful γ,γ-diboryl ketones. The development of geminal diborons as soft pronucleophiles also enabled their use as acyl anion equivalents via a one-pot tandem conjugate addition-oxidation sequence.
α-硼稳定碳负离子的共轭加成是一种研究不足的反应类型。现有的方法需要偕二/三硼烷的脱硼以及额外的活化基团的存在。我们报告了通过相应的偕二硼烷的去质子化生成的α,α-二硼碳负离子的 1,4-加成。该方法为高度取代和合成有用的γ,γ-二硼基酮提供了一般途径。偕二硼烷作为软亲核试剂的发展也使得它们可以通过一锅串联共轭加成-氧化序列用作酰基阴离子等价物。
