Merging C-H Activation and Strain-Release in Ruthenium-Catalyzed Isoindolinone Synthesis.

The merger of strain-release of 1,2-oxazetidines with carboxylic acid directed C-H activation in catalytic synthesis of isoindolinones is reported for the first time. This reaction opens a new and sustainable avenue to prepare a range of structurally diverse isoindolinone skeletons from readily available benzoic acids. The success of late-stage functionalization of some bioactive acids, and concise synthesis of biologically important skeletons demonstrated its great synthetic potential in drug discovery. Mechanistic studies indicated a plausible C-H activation/ß-carbon elimination/intramolecular cyclization cascade pathway.

Ru-catalysed C(sp2)-H vinylation/annulation of benzoic acids and alkynes: rapid access to medium-sized lactones.

An unprecedented ruthenium catalysed [4+4] annulation of readily available benzoic acids and alkynes is reported for the first time. The carboxylate group acts as both a directing group and an internal nucleophilic reagent to facilitate a C(sp2)-H vinylation/annulation cascade. This reaction avoids the classically oxidative [4+2] annulation, allowing the efficient synthesis of a wide array of eight-membered lactones under oxidant-free conditions. Moreover, this catalytic system can be successfully extended to [4+3] and [4+5] annulations for the assembly of seven- and nine-membered lactones.

Single Electron Activation of Aryl Carboxylic Acids.

Aryl carboxylic acids are stable and readily available in great structural diversity both from natural and well-established synthetic procedures, which make them promising starting materials in organic synthesis. The conversion of benzoic acids into high-value molecules is of great importance and have gained much interest of synthetic chemists. The recent development of single-electron (1e-) activation strategy has been esteemed as a complementary method for the transformation of benzoic acids. In this context, carboxylate groups can be selectively transferred into reactive aryl carboxylic radical, aryl radical, and acyl radical by electrocatalysis, photocatalysis, or in the presence of some SET oxidants. Based on these radical species, remarkable advancements have been achieved for the rapid formation of various chemical bonds over the past 10 years. In this review, we summarize recent advances in single electron activation of aryl carboxylic acids, with an emphasis on reaction scope, catalytic system, limitation, and underlying reaction mechanism.