Harabuchi Yu, Hayashi Hiroki, Takano Hideaki, Mita Tsuyoshi, Maeda Satoshi
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan.
JST, ERATO Maeda Artificial Intelligence in Chemical Reaction Design and Discovery Project, Kita 10, Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.
Angew Chem Int Ed Engl. 2023 Jan 2;62(1):e202211936. doi: 10.1002/anie.202211936. Epub 2022 Nov 28.
Systematic reaction path exploration revealed the entire mechanism of Knowles's light-promoted catalytic intramolecular hydroamination. Bond formation/cleavage competes with single electron transfer (SET) between the catalyst and substrate. These processes are described by adiabatic processes through transition states in an electronic state and non-radiative transitions through the seam of crossings (SX) between different electronic states. This study determined the energetically favorable SET path by introducing a practical computational model representing SET as non-adiabatic transitions via SXs between substrate's potential energy surfaces for different charge states adjusted based on the catalyst's redox potential. Calculations showed that the reduction and proton shuttle process proceeded concertedly. Also, the relative importance of SET paths (giving the product and leading back to the reactant) varies depending on the catalyst's redox potential, affecting the yield.
系统的反应路径探索揭示了诺尔斯光促进催化分子内氢胺化的完整机理。键的形成/断裂与催化剂和底物之间的单电子转移（SET）相互竞争。这些过程通过电子态中的过渡态的绝热过程以及不同电子态之间通过交叉缝（SX）的非辐射跃迁来描述。本研究通过引入一个实用的计算模型确定了能量上有利的SET路径，该模型将SET表示为通过SX在基于催化剂氧化还原电位调整的不同电荷状态的底物势能面之间的非绝热跃迁。计算表明，还原和质子穿梭过程协同进行。此外，SET路径（生成产物并回到反应物）的相对重要性因催化剂的氧化还原电位而异，从而影响产率。
