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Diene hydroaminomethylation via ruthenium-catalyzed C-C bond forming transfer hydrogenation: beyond carbonylation.

ABSTRACT: Under the conditions of ruthenium catalyzed transfer hydrogenation using 2-propanol as terminal reductant, 1,3-dienes engage in reductive C-C coupling with formaldimines obtained in situ from 1,3,5-tris(aryl)-hexahydro-1,3,5-triazines to form homoallylic amines. Deuterium labelling studies corroborate a mechanism involving reversible diene hydroruthenation to form an allylruthenium complex that engages in turn-over limiting imine addition. Protonolysis of the resulting amidoruthenium species releases product and delivers a ruthenium alkoxide, which upon ?-hydride elimination closes the catalytic cycle. These transformations, which include enantioselective variants, represent the first examples of diene hydroaminomethylation.

SUBMITTER: Oda S

PROVIDER: S-EPMC5950558 | biostudies-literature | 2016 Jan

REPOSITORIES: biostudies-literature

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Diene hydroaminomethylation <i>via</i> ruthenium-catalyzed C-C bond forming transfer hydrogenation: beyond carbonylation.

Oda Susumu S Franke Jana J Krische Michael J MJ

Chemical science 20151117 1

Under the conditions of ruthenium catalyzed transfer hydrogenation using 2-propanol as terminal reductant, 1,3-dienes engage in reductive C-C coupling with formaldimines obtained <i>in situ</i> from 1,3,5-tris(aryl)-hexahydro-1,3,5-triazines to form homoallylic amines. Deuterium labelling studies corroborate a mechanism involving reversible diene hydroruthenation to form an allylruthenium complex that engages in turn-over limiting imine addition. Protonolysis of the resulting amidoruthenium spec ...[more]

PMID: 29861974

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