Cs₂CO₃‐Catalyzed Aerobic Oxidative Cross‐Dehydrogenative Coupling of Thiols with Phosphonates and Arenes

Abstract

An efficient Cs CO -catalyzed oxidative coupling of thiols with phosphonates and arenes that uses molecular oxygen as the oxidant is described. These reactions provide not only a novel alkali metal salt catalyzed aerobic oxidation, but also an efficient approach to thiophosphates and sulfenylarenes, which are ubiquitously found in pharmaceuticals and pesticides. The reaction proceeds under simple and mild reaction conditions, tolerates a wide range of functional groups, and is applicable to the late-stage synthesis and modification of bioactive molecules.

Visible-Light-Promoted C–S Cross-Coupling via Intermolecular Charge Transfer

“…1e Therefore, the development of environmentally friendly and atom-economical methods for constructing C–S bonds is of significant importance with broad impact across the areas of small-molecule synthesis and materials. 2 …”

Iodide‐Catalyzed Phosphorothiolation of Heteroarenes Using P(O)H Compounds and Elemental Sulfur

“…[5b-d] In recent two years, Han and Jiao reported the direct dehydrogenative coupling of P (O)H groups with thiols. [6] Wu, Cui, Hong and Kumaraswamy developed the sulfenylation of Hphosphonates with arylsulfonyl derivatives. [7] In 2009, our group reported the direct coupling of P(O)H compounds with diaryl disulfides in the presence of catalytic amounts of copper iodide.…”

Hydrogen‐Bonding‐Network‐Assisted Regioselective Trifluoromethylthiolation and Sulfenylation of Electron‐Rich (Hetero)arenes

“…The regioselective formation of a CÀ S bond for the synthesis of organosulfur compounds is also a significant topic in the synthesis of materials and pharmaceuticals. [15] Recently, direct sulfenylation of electron-rich arenes such as indoles with sulfenyl halides, [16] N-thioimides, [17] thiols, [18] disulfides [19] has received much attention. Encouraged by our success of trifluoromethylthiolation of electron-rich arenes and indoles, we then investigated the reactions of sulfenylation under the optimized conditions (Scheme 3).…”