Shambhavi Chikkabagilu Nagaraju, Jeganmohan Masilamani
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, Tamil Nadu, India.
J Org Chem. 2022 Oct 7;87(19):13236-13258. doi: 10.1021/acs.joc.2c01730. Epub 2022 Sep 21.
A Rh(III)-catalyzed weak enone carbonyl/ketone-assisted aerobic oxidative C-H olefination of aromatics with unactivated alkenes has been developed. This protocol involves cross-dehydrogenative Heck-type olefination reaction of various substituted biologically relevant chalcones and aromatic ketones such as acetophenones and chromones with various functionalized unactivated olefins in moderate to good yields. Further, -alkylation of chalcones with norbornene is also demonstrated. A possible reaction mechanism involving weak chelation-assisted C-H activation/insertion/β-hydride elimination was proposed and supported by the deuterium labeling studies.
已开发出一种铑（III）催化的弱烯酮羰基/酮辅助的芳烃与未活化烯烃的需氧氧化C-H烯基化反应。该方案涉及各种取代的具有生物学相关性的查耳酮和芳族酮（如苯乙酮和色酮）与各种官能化的未活化烯烃的交叉脱氢Heck型烯基化反应，产率中等至良好。此外，还展示了查耳酮与降冰片烯的α-烷基化反应。提出了一种可能的反应机理，涉及弱螯合辅助的C-H活化/插入/β-氢化物消除，并得到氘标记研究的支持。
