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. 2016 Jan 1;7(1):136-141.
doi: 10.1039/c5sc03854e. Epub 2015 Nov 17.

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

Susumu Oda  1 , Jana Franke  1 , Michael J Krische  1
Affiliations

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

Susumu Oda et al. Chem Sci. .

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 β-hydride elimination closes the catalytic cycle. These transformations, which include enantioselective variants, represent the first examples of diene hydroaminomethylation.

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Figures

Scheme 1
Scheme 1. Hydroaminomethylation via carbonylation or 2-propanol mediated reductive coupling.
Scheme 2
Scheme 2. Conversion of hydroaminomethylation products 3b and 3i to compounds 4b and 4i, respectively. aYields are of material isolated by silica gel chromatography. (a) (HO)2CCO2H, MeCN–H2O, 25 °C, 80% yield, 10 : 1 dr (b) BrCH2CHCH2, K2CO3, DMF, 25 °C, 75% yield. (c) Grubbs-II, DCM, 40 °C, 72% yield. See ESI for further experimental details.
Scheme 3
Scheme 3. Enantioselective ruthenium catalyzed hydroaminomethylation of butadiene 1a and isoprene 1b. aYields are of material isolated by silica gel chromatography. Enantiomeric ratios were determined by chiral stationary phase HPLC analysis. bXylene (0.5 M), 140 °C. See ESI for further experimental details.
Scheme 4
Scheme 4. Deuterium labelling studies of the ruthenium catalyzed hydroaminomethylation of isoprene 1b. aYields are of material isolated by silica gel chromatography. bXylene (0.5 M), 140 °C. See ESI for further experimental details.
Scheme 5
Scheme 5. General mechanism for ruthenium catalyzed diene hydroaminomethylation via transfer hydrogenation.
See this image and copyright information in PMC

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