Molecular catalysis (2021)
Update date:2022-09-26
Topics:
Bényei, Attila C.
Bakos, József
Balogh, Szabolcs
Farkas, Gergely
Guóth, Mária
Major, Máté M.
Simon, József
Six novel thioether-aminophosphine type ligands with a general formula (Ar1)2PN(R1)CHR2(CH2)nCH(R3)SAr2 has been synthesized. The modular structure of the ligands and the new methodologies developed for their preparation enabled the systematic variation of their bridge length (n = 0 or 1), the substitution pattern of the backbone (R2, R3 = H or Me) as well as the P-, N- and S-substituents (Ar1 = Ph or 3,5-Me2C6H3, R1 = Et or iPr and Ar2 = Ph, 4-MeC6H4, or 4-MeOC6H4, respectively). The ligands proved to be effective in Pd-catalyzed asymmetric allylic etherification reactions providing the products in high yields (up to 95%) and with good enantioselectivities (up to 86%) using unprecedentedly low (0.2 mol%) loadings of the chiral Pd-catalyst. Based on these findings, a new scalable protocol has been developed for the preparation of chiral allylic ethers. Furthermore, the Pd(II) coordination chemistry of the ligands was thoroughly investigated by 1D and 2D NMR methods as well as by X-ray crystallography with special attention to the conformation of the chelate ring and the stereoselectivity of the sulfur coordination. Based on these studies, the main factors determining activity and selectivity of the catalytic system have been identified.
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