Despite the wide synthetic and industrial employment of hydrofunctionalization processes, the selective addition of S–H bonds across unsaturated C­–C bonds remains largely underdeveloped. Metal-catalyzed hydrothiolation is particularly challenging because sulfur reagents are known to poison transition metals. Nonetheless, we have developed a [Rh]-catalyzed, atom-economical route to install C–S bonds into electronically unbiased olefins with high degrees of regio-, chemo- and diastereoselectivity. We employ terminal olefins with tethered Lewis-basic functionality (i.e. amines or imines) to (1) increase the relative concentration of olefin to the metal, (2) prevent catalyst poisoning in the presence of nucleophilic thiols, (3) induce regioselectivity by preferentially forming one metallocycle intermediate, and (4) preclude beta-hydride elimination by prohibiting the necessary syn-periplanar geometry. Excitingly, this [Rh]-catalyzed system is regiodivergent; i.e., from common starting materials, we can access 1,2- or 1,3-amino thioethers by merely varying the phosphine ligand. Fortunately, aryl and alkyl thiols can be installed. Finally, the methodology can be used on electron-rich, electron-poor, and sterically-encumbered N-allyl Lewis bases with isolated yields up to 87% with &gt;20:1 regio- and diastereoselectivity.

Ligand-controlled, regiodivergent hydrothiolation: A [Rh]-catalyzed pathway to selectively form 1,2- and 1,3-amino thioethers

251st National Meeting (2016)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.