Panda Surajit, Saha Ratnakar, Sethi Subrat, Ghosh Rahul, Bagh Bidraha
School of Chemical Sciences, National Institute of Science Education and Research (NISER), HBNI, PO Bhimpur-Padanpur, Via Jatni, District Khurda, Bhubaneswar, Odisha 752050, India.
J Org Chem. 2020 Dec 4;85(23):15610-15621. doi: 10.1021/acs.joc.0c02400. Epub 2020 Nov 16.
A well-defined and readily available air-stable dimeric iridium(III) complex catalyzed α-alkylation of arylacetonitriles using secondary alcohols with the liberation of water as the only byproduct is reported. The α-alkylations were efficiently performed at 120 °C under solvent-free conditions with very low (0.1-0.01 mol %) catalyst loading. Various secondary alcohols including cyclic and acyclic alcohols and a wide variety of arylacetonitriles bearing different functional groups were converted into the corresponding α-alkylated products in good yields. Mechanistic study revealed that the reaction proceeds via alcohol activation by metal-ligand cooperation with the formation of reactive iridium-hydride species.
据报道，一种定义明确且易于获得的空气稳定二聚铱（III）配合物，能催化芳基乙腈与仲醇发生α-烷基化反应，且仅以水作为副产物释放出来。在无溶剂条件下，于120℃以极低（0.1 - 0.01 mol%）的催化剂负载量高效进行α-烷基化反应。包括环状和非环状醇在内的各种仲醇以及带有不同官能团的多种芳基乙腈，都能以良好的产率转化为相应的α-烷基化产物。机理研究表明，该反应通过金属-配体协同作用活化醇，形成活性铱氢物种来进行。
