Using hyperpolarised NMR and DFT to rationalise the unexpected hydrogenation of quinazoline to 3,4-dihydroquinazoline

Richards, Josh E., Alexander J. J. Hooper, Oliver W. Bayfield, Martin C. R. Cockett, Gordon J. Dear, A. Jonathon Holmes, Richard O. John, et al. “Using Hyperpolarised NMR and DFT to Rationalise the Unexpected Hydrogenation of Quinazoline to 3,4-Dihydroquinazoline.” Chemical Communications 54, no. 73 (2018): 10375–78.

PHIP and SABRE hyperpolarized NMR methods are used to follow the unexpected metal-catalysed hydrogenation of quinazoline (Qu) to 3,4-dihydroquinazoline as the sole product. A solution of [IrCl(IMes)(COD)] in dichloromethane reacts with H2 and Qu to form [IrCl(H)2(IMes)(Qu)2] (2). The addition of methanol then results in its conversion to [Ir(H)2(IMes)(Qu)3]Cl (3) which catalyses the hydrogenation reaction. Density functional theory calculations are used to rationalise a proposed outer sphere mechanism in which (3) converts to [IrCl(H)2(H2)(IMes)(Qu)2]Cl (4) and neutral [Ir(H)3(IMes)(Qu)2](6), both of which are involved in the formation of 3,4-dihydroquinazoline via the stepwise transfer of H+ and H, withH2 identified as the reductant. Successive ligand exchange in 3 results in the production of thermodynamically stable [Ir(H)2(IMes)(3,4-dihydroquinazoline)3]Cl (5).

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