A dimeric gold-catalyzed oxidative cross-coupling of arylboronates and arylsilanes has been developed for the synthesis of a large variety of biaryl compounds (>60 examples) and with broad versatility. It can overcome gold-catalyzed o,porientation rules of electron-rich arenes via C-H bond activation. This protocol has excellent functional-group tolerance and flexible synthetic capability for pharmacophores.

Development of catalytic amide bond-forming methods is important because they could potentially address the existing limitations of classical methods using superstoichiometric activating reagents. In this paper, we disclose an Umpolung amidation reaction of carboxylic acids with nitroarenes and nitroalkanes enabled by the triplet synergistic catalysis of FeI2, P(V)/P(III) and photoredox catalysis, which avoids the production of byproducts from stoichiometric coupling reagents. A wide range of carboxylic acids, including aliphatic, aromatic and alkenyl acids participate smoothly in such reactions, generating structurally diverse amides in good yields (86 examples, up to 97% yield). This Umpolung amidation strategy opens a method to address challenging regioselectivity issues between nucleophilic functional groups, and complements the functional group compatibility of the classical amidation protocols. The synthetic robustness of the reaction is demonstrated by late-stage modification of complex molecules and gram-scale applications.

In this paper, we report a moderate and practical method for precise deuteration of aliphatic carboxylic acids by synergistic photoredox and HAT catalysis. The reaction delivers excellent D-incorporation (up to...

Dual C-H thiolation reactions using elemental sulphur remain a challenge. This communication discloses an oxidative radical dual sp/sp C-H thiolation strategy for the coupling of imidazopyridines with ethers or alkanes using elemental sulphur.