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<p>The functionalization of alkenes is a practical and important approach to access high value-added compounds. We herein realized the combination of energy transfer (EnT) and hydrogen atom transfer (HAT) process for the <i>in situ</i> giving acyl azolium ions from the acyl electrophiles and <i>N</i>-heterocyclic carbenes (NHCs) catalysts under light irradiation, and developed three-component radical relay-type alkylacylation of readily available alkenes promoted by the cooperative NHC-photo cocatalysis to access structurally diversified alkylacylation products. The unique strategy for the NHC catalyst-bound acyl azoliums working as the intermolecular HAT reagent with the EnT process was revealed. This protocol was also utilized to enable the late-stage functionalization of some important drugs and bioactive molecules. It featured readily bifunctionalization of alkenes, a wide range of alkenes and acyl imidazoles, mild reaction conditions, excellent selectivity, as well as broad functional group compatibility. Scale-up synthesis and a list of derivatization reactions displayed the potential synthetic application. Control experimental investigations and computational studies support that it involved the photoexcitation of <i>in situ</i> forming acyl azolium ions via EnT process to access triplet diradical species with facile intersystem crossing, and acted as HAT reagents to undergo intermolecular HAT process, and then engaged in the following radical addition/radical-radical cross-coupling reaction with NHCs-linked radicals, resulting in alkylacylation products promoted by cooperative NHC and photocatalysis.</p>

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Cooperative N-heterocyclic carbenes and photocatalysis for the three-component alkylacylation of alkenes: divergent ketone synthesis

  • 期刊论文

  • 发表日期：

    2025年7月22日

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  • Kui Tian,
  • Fengrui Xiang,
  • Jin-Long Huang,
  • Yao-Wen Song,
  • Minyan Wang,
  • Chun-Jiang Wang,
  • Xiu-Qin Dong

摘要

The functionalization of alkenes is a practical and important approach to access high value-added compounds. We herein realized the combination of energy transfer (EnT) and hydrogen atom transfer (HAT) process for the in situ giving acyl azolium ions from the acyl electrophiles and N-heterocyclic carbenes (NHCs) catalysts under light irradiation, and developed three-component radical relay-type alkylacylation of readily available alkenes promoted by the cooperative NHC-photo cocatalysis to access structurally diversified alkylacylation products. The unique strategy for the NHC catalyst-bound acyl azoliums working as the intermolecular HAT reagent with the EnT process was revealed. This protocol was also utilized to enable the late-stage functionalization of some important drugs and bioactive molecules. It featured readily bifunctionalization of alkenes, a wide range of alkenes and acyl imidazoles, mild reaction conditions, excellent selectivity, as well as broad functional group compatibility. Scale-up synthesis and a list of derivatization reactions displayed the potential synthetic application. Control experimental investigations and computational studies support that it involved the photoexcitation of in situ forming acyl azolium ions via EnT process to access triplet diradical species with facile intersystem crossing, and acted as HAT reagents to undergo intermolecular HAT process, and then engaged in the following radical addition/radical-radical cross-coupling reaction with NHCs-linked radicals, resulting in alkylacylation products promoted by cooperative NHC and photocatalysis.