Mechanism of Rhodium-Catalyzed Formyl Activation: A Computational Study

The Journal of Organic Chemistry
Xiaoling LuoYu Lan

Abstract

Metal-catalyzed transfer hydroformylation is an important way of cleaving C-C bonds and constructing new double bonds. The newly reported density functional theory (DFT) method, M11-L, has been used to clarify the mechanism of the rhodium-catalyzed transfer hydroformylation reported by Dong et al. DFT calculations depict a deformylation and formylation reaction pathway. The deformylation step involves an oxidative addition to the formyl C-H bond, deprotonation with a counterion, decarbonylation, and β-hydride elimination. After olefin exchange, the formylation step takes place via olefin insertion into the Rh-H bond, carbonyl insertion, and a final protonation with the conjugate acid of the counterion. Theoretical calculations indicate that the alkalinity of the counterion is important for this reaction because both deprotonation and protonation occur during the catalytic cycle. A theoretical study into the formyl acceptor shows that the driving force of the reaction is correlated with the stability of the unsaturated bond in the acceptor. Our computational results suggest that alkynes or ring-strained olefins could be used as formyl acceptors in this reaction.

References

Dec 22, 1999·Angewandte Chemie·C P Lenges, M Brookhart
Dec 10, 2003·The Journal of Immunology : Official Journal of the American Association of Immunologists·Yoe-Sik BaeSung Ho Ryu
Sep 13, 2005·Biochemical and Biophysical Research Communications·Michael R Waterman, Galina I Lepesheva
Dec 21, 2005·Journal of Leukocyte Biology·Huamei FuClaes Dahlgren
Sep 12, 2006·Biochimica Et Biophysica Acta·Galina I Lepesheva, Michael R Waterman
Feb 29, 2008·Journal of the American Chemical Society·Peter FristrupRobert Madsen
Oct 30, 2010·Journal of the American Chemical Society·Diem H T PhanVy M Dong
Jan 28, 2012·Journal of the American Chemical Society·Tendai GadzikwaJoost N H Reek
Apr 21, 2012·Journal of the American Chemical Society·Qinggang HeSanjeev Mukerjee
Oct 30, 2012·Journal of the American Chemical Society·Nidhi TibrewalJürgen Rohr
Jan 25, 2013·Nature Chemistry·Terry P LeboldRichmond Sarpong
Mar 30, 2013·Science·Michael T PirnotDavid W C MacMillan
Oct 7, 2014·Chemistry : a European Journal·Dong LiuAiwen Lei
May 23, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiaotian QiYu Lan
Jun 20, 2015·Angewandte Chemie·Shuhei KusumotoKyoko Nozaki
Aug 14, 2012·Journal of Chemical Theory and Computation·Yan ZhaoDonald G Truhlar
Jul 1, 2008·Journal of Chemical Theory and Computation·Lindsay E RoyRichard L Martin

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Citations

Dec 2, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Lingli HanTao Liu
Jan 5, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiaoyu YueYu Lan
Aug 8, 2018·Journal of the American Chemical Society·Xuesong WuVy M Dong
Nov 8, 2017·Accounts of Chemical Research·Xiaotian QiYu Lan

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