Photoinduced Regiodivergent and Enantioselective Cross-Coupling of Glycine Derivatives with Hydrocarbon Feedstocks.

Regiodivergent asymmetric synthesis represents a transformative strategy for the efficient generation of structurally diverse chiral products from a single set of starting materials, significantly enriching their enantiomeric composition. However, the design of radical-mediated regiodivergent and enantioselective reactions that can accommodate a wide range of functional groups and substrates has posed significant challenges. The obstacles primarily lie in switching the regioselectivity and achieving high enantiodiscrimination, especially when dealing with high-energy intermediates.

Recent advances in theoretical studies on transition-metal-catalyzed regioselective C-H functionalization of indoles.

Indole compounds are widely found in natural products and drug candidates. The transition-metal-catalyzed regioselective C-H bond functionalization of indoles as the most efficient method for the synthesis of various functionalized indoles has been extensively studied in the past two decades due to its advantages of step economy and atom economy. In general, the catalysts included the transition-metals (Pd, Rh, Ru, Cu, Co, Fe, Zn, and Ga) and these reactions were accomplished with a remarkably wide range of coupling reagents for construction of various C-C and C-X (X = N, O, S) bonds.

Computational Chemistry-Assisted Highly Selective Radical Cascade Cyclization of 1,6-Enynes with Thiols: Access to Sulfur-Substituted 4-Enyl-2-Pyrrolidones.

In this study, an efficient method for the synthesis of sulfur-substituted 4-enyl-2-pyrrolidones was successfully developed through AIBN-promoted highly selective 5-exo-dig radical cascade cyclization of 1,6-enynes with sulfur sources with the aid of theoretical and computational chemistry. This protocol enables the first practical and green synthesis of an array of 4-enyl-2-pyrrolidones in moderate-to-good yields with broad substrate scopes and high regioselectivities (>20:1). Moreover, excellent stereoselectivities have also been achieved (up to >20:1, /).