Copper Hydride-Catalyzed Net Hydroformylation of Unactivated Terminal Olefins
We report a copper-catalyzed method for the highly regioselective formal hydroformylation via hydroacetalization of simple terminal alkenes. The robust protocol employs a commercially available diethoxy methyl ester proelectrophile activated by cocatalytic Zn(OTf)<sub>2</sub> and was found to operate on a variety of functionalized olefin substrates to provide acetal products with exclusive linear regioselectivity. Density functional theory studies support that the key C-C bond forming event between the alkyl copper and the oxocarbenium ion intermediates takes place via a frontside electrophilic substitution (S<sub>E</sub>2) mechanism with retention of configuration of the reacting Cu-C bond.
Authors
- Yuyang Dong (ORCID: https://orcid.org/0000-0002-4533-4798)
- Peng Liu (ORCID: https://orcid.org/0000-0002-8188-632X)
- Stephen L. Buchwald (ORCID: https://orcid.org/0000-0003-3875-4775)
- Subhash Garhwal (ORCID: https://orcid.org/0000-0002-0093-9224)
- Binh Khanh Mai (ORCID: https://orcid.org/0000-0001-8487-1417)
Institutions
- University of Pittsburgh (US)
- Massachusetts Institute of Technology (US)
Publication Details
- Journal
- Organic Letters
- Published
- 2025-07-26
- DOI
- https://doi.org/10.1021/acs.orglett.5c02708
- Primary Topic
- Organometallic Complex Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Institute of General Medical Sciences