2026-06-15 カリフォルニア大学サンタバーバラ校（UCSB）
＜関連情報＞
- https://news.ucsb.edu/2026/022651/yang-group-develops-new-mechanism-metal-carbene-radical-cross-coupling
- https://www.nature.com/articles/s41929-026-01532-9
外圏機構を介した有機ホウ素試薬とジアゾ化合物の立体選択的光金属生体触媒クロスカップリング Stereoselective photometallobiocatalytic cross-coupling of organoboron reagents and diazo compounds via an outer-sphere mechanism
Huanan Wang,Binh Khanh Mai,Chongtao Li,Xiao-Wang Chen,Rachel Weiss,Bryan Kudisch,Peng Liu & Yang Yang
Nature Catalysis Published:29 April 2026
DOI:https://doi.org/10.1038/s41929-026-01532-9
Abstract
Designing and developing synthetically useful biocatalytic reactions that operate through unconventional mechanisms represent a central challenge in modern biocatalysis research. By coupling photoredox catalysis and metalloenzyme catalysis, here we harness cooperative photometallobiocatalysis to merge enzymatically generated, open-shell iron carbenoids with reactive radical intermediates formed via excited-state chemistry. This strategy expands the scope of intermolecular radical C–C coupling reactions with excellent enantio- and diastereoselectivities. Central to the successful implementation of this design is the directed evolution of a small metalloprotein catalyst, derived from a thermophilic cytochrome c, to achieve challenging stereocontrol in radical C–C coupling via an outer-sphere mechanism. These photobiocatalytic, formal metal carbenoid–radical coupling reactions advance a distinct mode of stereoselective outer-sphere metal carbenoid chemistry, providing a powerful strategy to design and evolve biocatalytic C–C bond-forming reactions through otherwise challenging intermolecular asymmetric radical couplings.
