A Selective and General Cobalt‐Catalyzed Hydroaminomethylation of Olefins to Amines

Abstract

A new cobalt catalyst is presented for the domino hydroformylation-reductive amination reaction of olefins. The optimal Co-tert-BuPy-Xantphos catalyst shows good to excellent linear-to-branched (n/iso) regioselectivity for the reactions of aliphatic alkenes with aromatic amines under mild conditions. This system is far more selective than traditional cobalt(I) catalysts and even better than most known rhodium catalysts.

Hydroformylation of pyrolysis oils to aldehydes and alcohols from polyolefin waste

“…Pyrolysis oils generated from waste plastics can contain a number of other elements in both organic and inorganic forms, including N, O, Cl, Fe, Si, K, Ca, S, Zn, Cu, Ti, and Al (10). Catalytic hydroformylation is tolerant of several of these contaminants, which include carbonyls, ethers, alcohols, carboxamides, amines, silanes, siloxanes, halide salts, and iron impurities (19)(20)(21)(22)(23). Vinyl/allyl halides and conjugated diolefins ( 24) are expected to be catalyst poisons during hydroformylation and can be removed by pretreating waste plastics before pyrolysis or adjusting parameters in the plastic pyrolysis.…”

Industrially applied and relevant transformations of 1,3-butadiene using homogeneous catalysts

“…211,212 The resulting epoxide has been directly converted to 1,4-butanediol further on, or thermally rearranged to 2,5-dihydrofuran. In addition, numerous academically interesting functionalizations of 1,3-butadiene have been reported in recent years, including hydroboration, [213][214][215] hydrosilylation, [216][217][218] hydroamination, [219][220][221][222] etc. The exploration of these novel methodologies might provide more possibilities of converting 1,3-butadiene into industrially relevant chemicals in the future.…”

An improved cobalt-catalysed alkoxycarbonylation of olefins using secondary phosphine oxide promotors

“…10 The related Co-catalysed domino-hydroformylation-reductive amination reaction (hydroaminomethylation) of olefins with carbon monoxide, hydrogen and secondary anilines could also be catalysed under comparably mild conditions in the presence of specific bidentate phosphine ligands to give the corresponding amine products with high linear to branched ratio. 11…”

“…10 The related Co-catalysed domino-hydroformylation-reductive amination reaction (hydroaminomethylation) of olefins with carbon monoxide, hydrogen and secondary anilines could also be catalysed under comparably mild conditions in the presence of specific bidentate phosphine ligands to give the corresponding amine products with high linear to branched ratio. 11 Compared to cobalt-catalysed hydroformylations, carbonylations with other kinds of nucleophiles such as alcohols or water for ester or carboxylic acid preparation are rarely reported. More specifically, around four decades ago, two patents from BASF reported dimethyl adipate production from 1,3-butadiene using Co 2 (CO) 8 as pre-catalyst in the presence of pyridine at very high CO pressure and temperature.…”