meta-C-H olefination, arylation, and acetoxylation of indolines have been developed using nitrile-containing templates. The combination of a monoprotected amino acid ligand and the nitrile template attached at the indolinyl nitrogen via a sulfonamide linkage is crucial for the meta-selective C-H functionalization of electron-rich indolines that are otherwise highly reactive toward electrophilic palladation at the para-positions. A wide range of synthetically important and advanced indoline analogues are selectively functionalized at the meta-positions.
Clear elucidation of the oxidative relationships of the active metal hydroperoxide moiety with its corresponding metal oxo and hydroxo intermediates would help the understanding of the different roles they may play in redox metalloenzymes and oxidation chemistry. Using an Mn(Me(2)EBC)Cl(2) complex, it was found that, in t-butanol-water (4 : 1) with excess H(2)O(2) at pH 1.5, the Mn(IV)-OOH moiety may exist in the catalytic solution with a mass signal of m/z = 358.1, which provides a particular chance to investigate its oxidative properties. In catalytic oxidations, the Mn(IV)-OOH moiety demonstrates a relatively poor activity in hydrogen abstraction from diphenyl methane and ethylbenzene with TOF of only 1.2 h(-1) and 1.1 h(-1) at 50 °C, whereas it can efficiently oxygenate diphenyl sulfide, methyl phenyl sulfide and benzyl phenyl sulfide with TOF of 13.8 h(-1), 15.4 h(-1) and 17.8 h(-1), respectively. In mechanistic studies using H(2)(18)O and H(2)(18)O(2), it was found that, in the Mn(IV)-OOH moiety mediated hydrogen abstraction and sulfide oxygenations, the reaction proceeds by two parallel pathways: one by direct oxygen insertion/transfer, and the other by plausible electron transfer. Together with a good understanding of the corresponding manganese(IV) oxo and hydroxo intermediates, this work provides the first chance to compare the reactivity differences and similarities of the active metal oxo, hydroxo and hydroperoxide intermediates. The available evidence reveals that the Mn(IV)-OOH moiety has a much more powerful oxidizing capability than the corresponding Mn(IV)=O and Mn(IV)-OH functional groups in both hydrogen abstraction and oxygenation.
The Mn+OH moiety in a manganese(IV) complex has more powerful electron‐transfer capability than its corresponding Mn+O moiety. An Mn+O moiety can abstract hydrogen from a substrate, then rebind the OH group from its reduced M(n−1)+OH form to the substrate radical. In contrast, the active center with an Mn+OH cannot perform similar rebound from its reduced M(n−1)+OH2 group (see scheme; HAT=hydrogen abstraction).
2,4,6-Trimethoxypyridine is identified as an efficient ligand for promoting a Pd-catalyzed ortho-C-H amination of both benzamides and triflyl-protected benzylamines. This finding provides guidance for the development of ligands that can improve or enable Pd(II)-catalyzed Csp2-H activation reactions directed by weakly coordinating functional groups.
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