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Computational Insights into the Mechanism of the Mo-Catalyzed Deoxygenative Coupling of Aromatic Aldehydes
Received date: 2024-05-14
Online published: 2024-05-30
Supported by
National Natural Science Foundation of China(22373073)
Mo/o-quinone complexes have shown great capability in promoting deoxygenation of carbonyl groups in the presence of appropriate reducing agents, which yields key Mo-carbene complexes and subsequently undergoes further transformations. However, the detailed mechanistic pathways for the deoxygenation of carbonyl groups with the assistance of additive remain unclear. Herein, a comprehensive density functional theory (DFT) study was performed to gain mechanistic insights into the Mo-catalyzed deoxygenative coupling of aromatic aldehydes to produce diaryl alkenes with the assistance of triphenylphosphine (PPh3) as a reductant. Computational results suggest that the Mo(IV) complex (with two o-quinone ligands) is more efficient than the commonly proposed Mo(II) complex (with one o-quinone ligand) in mediating the deoxygenation of aromatic aldehyde to yield a critical Mo-carbene intermediate. An outer-sphere stepwise mechanistic pathway is suggested for the PPh3 assisted deoxygenation of aromatic aldehyde, which proceeds through the generation of an adduct with aldehyde via P—O bond formation followed by the breaking of C—O bond of aldehyde to give the key Mo(IV)-carbene intermediate. The commonly proposed oxidative addition of carbonyl group onto Mo(II) to form an oxo-Mo-carbene intermediate might not be feasible. After the formation of the Schrock-type Mo(IV) carbene intermediate, a metathesis mechanistic pathway via a [2＋2] cycloaddition adduct is reasonable to afford the final product. The factors accounting for the formation of Mo(IV) carbene and the stereo-selectivity of the product are discussed.
Qinghao Sun , Xiaoguang Bao . Computational Insights into the Mechanism of the Mo-Catalyzed Deoxygenative Coupling of Aromatic Aldehydes[J]. Chinese Journal of Organic Chemistry, 2024 , 44(11) : 3518 -3525 . DOI: 10.6023/cjoc202405018
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