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Theoretical Investigation of the Mechanism of Rh(III)-catalyzed Annulation of 2-Biphenylboronic Acid with Activated Alkene

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Abstract

The mechanism is investigated for CptBuRh(OH)2-catalyzed annulation of 2-biphenylboronic acid with three activated alkenes using M06-2X functional. The reaction comprises transmetalation via two steps and following C-H activation producing reactive Rh-biphenyl complex with two Rh—C σ bonds. After the coordination/insertion of alkenes, respective fused or bridged cyclic products are yielded depending on different alkenes accompanied by the release of CptBuRh. The promotion of CptBuRh(OH)2 lies in the barrier decrease of transmetalation and C-H activation ready for coordination/insertion ensuring the smooth progress of common rate-limiting reductive elimination. The stereoselective transfer and ring rotation are specific for benzoquinone and cyclopropenone. The role of Rh(III) catalyst and release of Rh(I) is supported by Multiwfn analysis on frontier molecular orbital(FMO) of specific transiton states(TSs) and Mayer bond order(MBO) value of vital bonding, breaking.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos.21973056, 21972079), the Natural Science Foundation of Shandong Province, China(No.ZR2019MB050) and the Project of the Key Laboratory of Agricultural Film Application of Ministry of Agriculture and Rural Affairs, China.

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Authors and Affiliations

  1. College of Chemistry and Material Science, Shandong Agricultural University, Taian, 271018, P. R. China

    Nan Lu, Chengxia Miao & Xiaozheng Lan

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  1. Nan Lu
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  2. Chengxia Miao
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  3. Xiaozheng Lan
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Correspondence to Nan Lu.

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40242_2022_2187_MOESM1_ESM.pdf

Theoretical investigation of the mechanism of Rh(III)-catalyzed annulation of 2-biphenylboronic acid with activated alkene

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Lu, N., Miao, C. & Lan, X. Theoretical Investigation of the Mechanism of Rh(III)-catalyzed Annulation of 2-Biphenylboronic Acid with Activated Alkene. Chem. Res. Chin. Univ. 39, 276–282 (2023). https://doi.org/10.1007/s40242-022-2187-6

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  • DOI: https://doi.org/10.1007/s40242-022-2187-6

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