Alcohol Synthesis by Cobalt-Catalyzed Visible-Light-Driven Reductive Hydroformylation

Connor S. MacNeil; Lauren N. Mendelsohn; Tyler P. Pabst; Gabriele Hierlmeier; Paul J. Chirik

doi:10.1021/jacs.2c07745

Alcohol Synthesis by Cobalt-Catalyzed Visible-Light-Driven Reductive Hydroformylation

Connor S. MacNeil, Lauren N. Mendelsohn, Tyler P. Pabst, Gabriele Hierlmeier, Paul J. Chirik

Chemistry

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

A cobalt-catalyzed reductive hydroformylation of terminal and 1,1-disubstituted alkenes is described. One-carbon homologated alcohols were synthesized directly from CO and H₂, affording anti-Markovnikov products (34−87% yield) with exclusive regiocontrol (linear/branch >99:1) for minimally functionalized alkenes. Irradiation of the air-stable cobalt hydride, (dcype)Co(CO)₂H (dcype = dicyclohexylphosphinoethane) with blue light generated the active catalyst that mediates alkene hydroformylation and subsequent aldehyde hydrogenation. Mechanistic origins of absolute regiocontrol were investigated by in situ monitoring of the tandem catalytic reaction using multinuclear NMR spectroscopy with syngas mixtures.

Original language	English (US)
Pages (from-to)	19219-19224
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	144
Issue number	42
DOIs	https://doi.org/10.1021/jacs.2c07745
State	Published - Oct 26 2022

All Science Journal Classification (ASJC) codes

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/jacs.2c07745

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title = "Alcohol Synthesis by Cobalt-Catalyzed Visible-Light-Driven Reductive Hydroformylation",

abstract = "A cobalt-catalyzed reductive hydroformylation of terminal and 1,1-disubstituted alkenes is described. One-carbon homologated alcohols were synthesized directly from CO and H2, affording anti-Markovnikov products (34−87% yield) with exclusive regiocontrol (linear/branch >99:1) for minimally functionalized alkenes. Irradiation of the air-stable cobalt hydride, (dcype)Co(CO)2H (dcype = dicyclohexylphosphinoethane) with blue light generated the active catalyst that mediates alkene hydroformylation and subsequent aldehyde hydrogenation. Mechanistic origins of absolute regiocontrol were investigated by in situ monitoring of the tandem catalytic reaction using multinuclear NMR spectroscopy with syngas mixtures.",

author = "MacNeil, {Connor S.} and Mendelsohn, {Lauren N.} and Pabst, {Tyler P.} and Gabriele Hierlmeier and Chirik, {Paul J.}",

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T1 - Alcohol Synthesis by Cobalt-Catalyzed Visible-Light-Driven Reductive Hydroformylation

AU - MacNeil, Connor S.

AU - Mendelsohn, Lauren N.

AU - Pabst, Tyler P.

AU - Hierlmeier, Gabriele

AU - Chirik, Paul J.

PY - 2022/10/26

Y1 - 2022/10/26

N2 - A cobalt-catalyzed reductive hydroformylation of terminal and 1,1-disubstituted alkenes is described. One-carbon homologated alcohols were synthesized directly from CO and H2, affording anti-Markovnikov products (34−87% yield) with exclusive regiocontrol (linear/branch >99:1) for minimally functionalized alkenes. Irradiation of the air-stable cobalt hydride, (dcype)Co(CO)2H (dcype = dicyclohexylphosphinoethane) with blue light generated the active catalyst that mediates alkene hydroformylation and subsequent aldehyde hydrogenation. Mechanistic origins of absolute regiocontrol were investigated by in situ monitoring of the tandem catalytic reaction using multinuclear NMR spectroscopy with syngas mixtures.

AB - A cobalt-catalyzed reductive hydroformylation of terminal and 1,1-disubstituted alkenes is described. One-carbon homologated alcohols were synthesized directly from CO and H2, affording anti-Markovnikov products (34−87% yield) with exclusive regiocontrol (linear/branch >99:1) for minimally functionalized alkenes. Irradiation of the air-stable cobalt hydride, (dcype)Co(CO)2H (dcype = dicyclohexylphosphinoethane) with blue light generated the active catalyst that mediates alkene hydroformylation and subsequent aldehyde hydrogenation. Mechanistic origins of absolute regiocontrol were investigated by in situ monitoring of the tandem catalytic reaction using multinuclear NMR spectroscopy with syngas mixtures.

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Alcohol Synthesis by Cobalt-Catalyzed Visible-Light-Driven Reductive Hydroformylation

Abstract

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