The recent literature on asymmetric hydroformylation is reviewed from the perspective of the ligand development. Much progress was made in the area of hybrid bidentate ligands containing one P-chiral phosphine...

C-H bond functionalization is a well-developed concept that has been thoroughly studied and gives entry to rather complex molecules without the need for previous derivatization of the substrates. The use of copper complexes in allylic C-H bond functionalization under oxidative conditions as an alternative to the well-established palladium-based methodologies remains largely underdeveloped. Here, we show for the first time a selective cross-dehydrogenative coupling reaction between underivatized allylic substrates and terminal alkynes to produce 1,4-enynes in high yields in a single step, using an in situ synthesized copper catalyst and an oxidant.

An efficient, novel photocatalyzed allylic-alkynylation methodology via copper-based cross-dehydrogenative coupling (CDC) is described. Different types of 1,4-enyne compounds were synthesized in one step at room temperature using copper(I) terpyridyl complex as photocatalyst/initiator. This procedure is an improvement and to some extent complementary to previously reported thermal CDC methods. Preliminary investigations on the reaction mechanism are also presented.

Hypervalent iodine(III) five‐membered heterocycles have found broad application as atom‐transfer reagents for organic synthesis. Among them, 1‐phenyl‐1,2‐benziodoxol‐3‐(1H)‐one is known as a traditional benzyne precursor, but no further synthetic applications have been reported. Herein, we report the first synthetic application of 1‐phenyl‐1,2‐benziodoxol‐3‐(1H)‐one to the synthesis of phthalides by using only CuI as catalyst. High selectivity and yields were achieved under mild reaction conditions with good functional group tolerance. During our investigations, the efficiency of different CuI and CuII catalysts under various reaction conditions were studied. The nature of the leaving group, the substituents on the substrate, and the temperature play an important role on both yield and selectivity. Moreover, a plausible mechanistic pathway for this transformation was proposed based on our observations and previous literature reports.

Reactions that form C–C bonds are at the heart of many important transformations, both in industry and in academia. From the myriad of catalytic approaches to achieve such transformations, those relying on C–H functionalization are gaining increasing interest due to their inherent sustainable nature. In this short review, we showcase the most recent advances in the field of C–C bond formation via C–H functionalization, but focusing only on those methodologies relying on copper catalysts. This coinage metal has gained increased popularity in recent years, not only because it is cheaper and more abundant than precious metals, but also thanks to its rich and versatile chemistry.1 Introduction2 Cross-Dehydrogenative Coupling under Thermal Conditions2.1 C(sp3)–C(sp3) Bond Formation2.2 C(sp3)–C(sp2) Bond Formation2.3 C(sp2)–C(sp2) Bond Formation2.4 C(sp3)–C(sp) Bond Formation3 Cross-Dehydrogenative Coupling under Photochemical Conditions3.1 C(sp3)–C(sp3) Bond Formation3.2 C(sp3)–C(sp2) and C(sp3)–C(sp) Bond Formation4 Conclusion and Perspective