Bulky Di(1-adamantyl)phosphinous Acid-Ligated Pd(II) Precatalysts for Suzuki Reactions of Unreactive Aryl Chlorides

ACS Omega. 2021 Dec 8;6(50):35134-35143. doi: 10.1021/acsomega.1c06430. eCollection 2021 Dec 21.

ABSTRACT

Di(1-adamantyl)phosphine oxide (SPO-Ad: Ad2P(V)(=O)H), a stable tautomer of di(1-adamantyl)phosphinous acid (PA-Ad: Ad2P(III)-OH), was employed to synthesize two new PA-Ad-coordinated complexes, POPd-Ad and POPd2-Ad. POPd-Ad was easily transformed from POPd2-Ad in acetonitrile, and the [M – H]- ion of the deprotonated POPd-Ad was observed in the electrospray ionization-mass spectrum of POPd2-Ad. Both complexes are effective precatalysts for the Suzuki reaction of aryl chlorides. The reduction of Pd(II) in POPd-Ad and POPd2-Ad by arylboronic acid was examined, and the ideal Pd-to-PA ratio in the Suzuki reaction was found to be 1:1. The effect of temperature on the catalytic yields was studied to examine the possible ligation state of the active species and the dimer-to-monomer process of POPd2-Ad. Mononuclear and mono-ligated Pd species was assumed to be catalytically active. The electronic and steric effects of PA-Ad were slightly better than those reported for PA-tBu ( t Bu2P(III)-OH). Density functional theory calculations were performed to evaluate the formation of mono-ligated and mononuclear Pd species from POPd-Ad and POPd2-Ad. Furthermore, the reaction time and catalyst loading could be reduced for the reported POPd1-tBu precatalyst using the optimized reaction conditions for POPd-Ad. The complexes synthesized in this extensive study will complement the existing SPO-coordinated POPd series of precatalysts.

PMID:34963994 | PMC:PMC8697604 | DOI:10.1021/acsomega.1c06430

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