Reported herein is the use of catalytic [{Ir(cod)Cl}2] to facilitate hydrogen-borrowing reactions of ketone enolates with methanol at 65 °C. An oxygen atmosphere accelerates the process, and when combined with the use of a bulky monodentate phosphine ligand, interrupts the catalytic cycle by preventing enone reduction. Subsequent addition of pro-nucleophiles to the reaction mixture allowed a one-pot methylenation/conjugate addition protocol to be developed, which greatly expands the range of products that can be made by this methodology.

We report the first boron-substituted naphthalenediimides (NDIs), prepared by iridium catalysed C-H activation. When the NDI substrates bear N-benzyl substituents, the naphthyl NDI core is borylated in preference, suggestive of a directed borylation mechanism. Borylated NDIs are substrates for Suzuki-Miyaura couplings and borylation of an NDI bearing two inequivalent N-substituents has also been demonstrated.

Reported herein is the use of catalytic [{Ir(cod)Cl} 2 ] to facilitate hydrogen-borrowing reactions of ketone enolates with methanol at 65 8C. An oxygen atmosphere accelerates the process, and when combined with the use of a bulky monodentate phosphine ligand, interrupts the catalytic cycle by preventing enone reduction. Subsequent addition of pronucleophiles to the reaction mixture allowed a one-pot methylenation/conjugate addition protocol to be developed, which greatly expands the range of products that can be made by this methodology.

No abstract

IrCl(cod)] 2 as the catalyst promotes hydrogen-borrowing reaction of ketone enolates with methanol to give enones (III) which can react with excess methanol as nucleophile to yield mixtures f methoxymethyl derivatives (IV) and the enones (III). The process can be extended to the subsequent coupling with nucleophiles to provide a one-pot methenylation/conjugate addition process. The use of the products for pyridine synthesis or Baeyer-Villiger type ester synthesis is also demonstrated. -(SHEN, D.; POOLE, D. L.; SHOTTON, C. C.; KORNAHRENS, A. F.; HEALY, M. P.; DONOHOE*, T. J.; Angew. Chem., Int. Ed. 54 (2015) 5, 1642-1645, http://dx.doi.org/10.1002/anie.201410391 ; Dep. Chem., Univ. Oxford, Oxford OX1 3TA, UK; Eng.) -Mais