H 2 O 2 -Mediated Oxidative S–H/P(O)–H Cross-Coupling to Access Thiophosphates

N/air-mediated dehydrogenative cross-coupling of thiols and trialkyl phosphites(III) have been developed for the construction of thiophosphates. These environmentally benign and mild strategies exhibited exceptional functional group compatibility and providing access to a wide array of S-P architectures (46 examples, yields up to 95%). Crucially, both methods feature operational simplicity, facile scalability, and direct applicability to bioactive molecule synthesis. Detailed mechanistic studies indicated that a radical pathway was involved in the synthesis of thiophosphates.