亚胺
化学
铜
醛
胺气处理
表面改性
区域选择性
催化作用
药物化学
组合化学
有机化学
物理化学
作者
Joe I. Higham,James A. Bull
标识
DOI:10.1002/anie.202202933
摘要
Transient directing groups (TDGs) can provide a powerful means for C-H functionalization without requiring additional steps for directing group introduction and removal. We report the first use of a TDG in combination with copper to effect C-H functionalization. The regioselective copper mediated β-C(sp2 )-H sulfonylation of aldehydes with sulfinate salts is accomplished using catalytic β-alanine to form a transient imine. A broad range of sulfonylated benzaldehydes are prepared using copper fluoride as both copper source and oxidant, involving a [5,6] cupracyclic intermediate. γ-(peri)-Sulfonylation of napthyl and phenanthrenyl carboxaldehydes is achieved through [6,6] cupracyclic intermediates. Further derivatisation of the aldehyde products is demonstrated. Kinetic experiments and Hammett analysis suggest the turnover limiting step to be a concerted asynchronous C-H cleavage via a dearomative Wheland-type transition state.
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