The role of hydrogen bonds in Baeyer-Villiger reactions.
The role of hydrogen bonds in Baeyer-Villiger reactions.
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DOI：
10.1021/jo0626562
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发表时间：
2007-03
期刊：
影响因子：
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通讯作者：
S. Yamabe;S. Yamazaki
中科院分区：
文献类型：
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作者：
S. Yamabe;S. Yamazaki
用密度泛函理论计算了不同的Baeyer-Villiger(B-V)氧化反应。讨论了过氧酸分子与酮的亲核加成(TS1)和O-O的迁移裂解(TS3)这两个关键步骤的过渡态(TSS)中的质子运动。在Criegee中间体(TS2)中发现了一个新的氢键重排TS。氢键的方向性需要在过氧酸分子与酮TS(TS1)的亲核加成反应中形成三聚体。在O-O-TS(TS3)的迁移-裂解过程中，还需要三个过氧酸分子。用(丙酮和(H-CO-OH)n，n=3)体系确定了B-V反应的基本过程。过氧酸分子与酮TS(TS1)的亲核加成反应和O-O TS(TS3)在参与的三聚体(n=3)中的迁移-裂解几何构型对过氧酸上的取代基几乎不敏感。方向性在这些几何中得到了满足。O-O-TS(TS3)的迁移-裂解反应[Me2C=O+(H-CO-OOH)3]、[Me2C=O+(F3C-CO-OH3)3]和[Me2C=O+(MCPBA)3]在反应中起决定作用。相反，过氧酸分子与酮(TS1)的亲核加成在反应中是速度决定的，[Ph(Me)C=O+(H-CO-OOH)3]。
Various Baeyer-Villiger (B-V) oxidation reactions were examined by density functional theory calculations. Proton movements in transition states (TSs) of the two key steps, the nucleophilic addition of a peroxyacid molecule to a ketone (TS1) and the migration-cleavage of O-O (TS3), were discussed. A new TS of a hydrogen-bond rearrangement in the Criegee intermediate (TS2) was found. The hydrogen-bond directionality requires a trimer of the peroxyacid molecules at the nucleophilic addition of a peroxyacid molecule to a ketone TS (TS1). At the migration-cleavage of O-O TS (TS3), also three peroxyacid molecules are needed. Elementary processes of the B-V reaction were determined by the use of the (acetone and (H-CO-OOH)n, n=3) system. The geometries of the nucleophilic addition of a peroxyacid molecule to a ketone TS (TS1) and the migration-cleavage of O-O TS (TS3) in the trimer (n=3) participating are nearly insensitive to the substituent on the peroxyacid. The directionality is satisfied in those geometries. The migration-cleavage of O-O TS (TS3) was found to be rate-determining in reactions, [Me2C=O+(H-CO-OOH)3], [Me2C=O+(F3C-CO-OOH)3], and [Me2C=O+(MCPBA)3]. In contrast, the nucleophilic addition of a peroxyacid molecule to a ketone (TS1) is rate-determining in the reaction, [Ph(Me)C=O+(H-CO-OOH)3].