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We took the proton transfer step (Path-f) as an example to investigate the influence of hydrogen bonding, and it turned out that hydrogen bonding induced by solvent is unlikely to occur. Please see ESI for details Mechanism Path-g was also examined in which C1-H bond of Int1 break first via TS-g. See the ESI for more details We have investigated the formation of the diastereomer of Int1 and the transition states for conversion of both diastereomers into Int2 and Int5. Detailed results are given in the ESI. Other three attack mode (1-Si, 4-Si), (1-Re, 4-Re), (1-Re, 4-Si) of Int5, and another three attack mode (1-Si, 4-Si), (1-Re, 4-Re), (1-Si, 4-Re) of Int2 in Stetter reaction are placed in ESI.
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