Formation of TEMPO Adducts with Hydrogen Atom Transfer: A New Pathway to Versatile Hydrofunctionalizations of Olefins
Year: 2024
Type: preprint
Abstract: Since the seminal work by Mukaiyama, many research groups reported hydrofunctionalization of olefin with different metal hydrides in situ. Despite the rapid development of MHAT (metal-catalyzed hydrogen atom transfer)-derived reactions, the need for using different catalyst systems to accommodate different reactivities makes it not appealing. Here, we describe a two-step process to access a broad range of hydrofunctionalization of olefins. The first step involves a cobalt-catalyzed formation of TEMPO adduct from olefins. The reaction demonstrates a broad substrate scope and functional group tolerance. The second step involves a photocatalytic nucleophilic addition to generate a new C-C, C-N, C-O, C-F, and C-Cl bond. Interestingly with our methodology, nucleophilic fluorination could be achieved with a short reaction time, showing its potential in PET applications. Combining the two steps, a net hydrofunctionalization of olefins with a broad range can be achieved by simply changing the nucleophiles in the second step. Noteworthily, a two-step diastereoselective hydration of olefins was also demonstrated by employing the bulkiness of TEMPO.
Source: ChemRxiv
Institution: Columbia University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W4391746165