Intermolecular Phosphite-Mediated Radical Desulfurative Alkene Alkylation Using Thiols

Abstract

<div><div><div><p>We report herein the development of an S-atom transfer process using triethyl phosphite as the S-atom acceptor that allows thiols to serve as precursors of C-centered radials. A range of functionalized and electronically unbiased alkenes including those containing common heteroatom-based functional groups. This process is driven by the exchange of relatively weak S-H and C-S bonds of aliphatic thiols for C-H, C-C, and S-P bonds of the products formed.</p></div></div></div>

Phosphoranyl Radical Fragmentation Reactions Driven by Photoredox Catalysis

“…The most common method for their formation is radical addition into a trivalent phosphorus species, typically a phosphine, or phosphite ( Scheme 3 A). 10 Alternatively, the equivalent phosphoranyl radical can also be generated via ionic attack of a trivalent phosphorus radical cation with a suitable nucleophile ( Scheme 3 B). 11 …”

Intermolecular Phosphite-Mediated Radical Desulfurative Alkene Alkylation Using Thiols

“…This process is driven by the cleavage of relatively weak S-H and C-S bonds of the starting materials (~89 and 78 kcal/mol, respectively) to form stronger P-S, C-C, and C-H bonds of the products (90, ~85, 98 kcal/mol). 29 In conclusion, we describe an S-atom transfer, phosphite-mediated reductively alkylation of a wide range of alkenes, including examples of those present in naturally occurring, biologically active compounds, using thiols as C-centered radical precursors. We demonstrate that a variety of 1° and 2° thiols adjacent to anion stabilizing groups serve as precursors to achieve C-C bond formation with olefins.…”