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Alcohol Synthesis by Cobalt-Catalyzed Visible-Light-Driven Reductive Hydroformylation
Connor S MacNeil1, Lauren N Mendelsohn1, Tyler P Pabst1
1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
Journal of the American Chemical Society
|October 14, 2022
Summary
Cobalt catalysts enable reductive hydroformylation of alkenes using carbon monoxide and hydrogen. This process yields anti-Markovnikov alcohols with high regioselectivity, offering a new synthetic route.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Organic Synthesis
Background:
- Hydroformylation is a key industrial process for converting alkenes to aldehydes.
- Developing selective and efficient catalytic systems remains an active area of research.
- Reductive hydroformylation offers a direct route to alcohols, bypassing aldehyde isolation.
Purpose of the Study:
- To describe a novel cobalt-catalyzed reductive hydroformylation of alkenes.
- To achieve high yields and exclusive regiocontrol in the synthesis of one-carbon homologated alcohols.
- To investigate the catalytic mechanism and origins of regioselectivity.
Main Methods:
- Utilizing a cobalt hydride complex, (dcype)Co(CO)2H, activated by blue light irradiation.
- Employing syngas (CO and H2) as the source of carbon monoxide and hydrogen.
- In situ multinuclear NMR spectroscopy for mechanistic investigations.
Main Results:
- Successful synthesis of one-carbon homologated alcohols from terminal and 1,1-disubstituted alkenes.
- Achieved anti-Markovnikov product formation with yields ranging from 34-87%.
- Demonstrated exclusive regiocontrol (linear/branch >99:1) for minimally functionalized alkenes.
Conclusions:
- The developed cobalt catalyst system provides an efficient method for reductive hydroformylation.
- The study elucidates the mechanistic basis for the observed absolute regiocontrol.
- This work presents a valuable new tool for synthesizing functionalized alcohols.
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