In the past decade, direct C-H arylation of indoles has been developed with high selectivity at the C2 and C3 positions via transition-metal-catalyzed cross-coupling reactions. Here we show that C-H activation can be directed to the C7 position with high selectivity in Pd-catalyzed coupling of indoles with arylboronic acids. The key to this high regioselectivity is the appropriate choice of a phosphinoyl directing group and a pyridine-type ligand in the presence of Pd(OAc)2 catalyst. This previously elusive transformation should provide insight for the design of other cross-couplings as well.
Modification of commercially available monophosphine ligands with either aryl bromides or chlorides by rhodium(I)-catalyzed, tertiary phosphine directed C-H activation is described. A series of ligand libraries containing mono- and diaryl-substituted groups, having different steric and electronic properties, were obtained in high yields. Based on the outstanding properties of their parent scaffolds, the modified ligands have been found to be powerful in organic reactions.
Cu2ZnSn(S1−xSex)4 nanocrystals are an emerging family of functional materials with huge potential of industrial applications, however, it is an extremely challenging task to synthesize Cu2ZnSn(S1−xSex)4 nanocrystals with both tunable energy band and phase purity. Here we show that a green and economic route could be designed for the synthesis of Cu2ZnSn(S1−xSex)4 nanocrystals with bandgap tunable in the range of 1.5–1.12 eV. Consequently, conduction band edge shifted from −3.9 eV to −4.61 eV (relative to vacuum energy) is realized. The phase purity of Cu2ZnSn(S1−xSex)4 nanocrystals is substantiated with in-depth combined optical and structural characterizations. Electrocatalytic and thermoelectric performances of Cu2ZnSn(S1−xSex)4 nanocrystals verify their superior activity to replace noble metal Pt and materials containing heavy metals. This green and economic route will promote large-scale application of Cu2ZnSn(S1−xSex)4 nanocrystals as solar cell materials, electrocatalysts, and thermoelectric materials.
Rhodium-catalyzed C7-selective decarbonylative arylation, olefination, and methylation of indoles with carboxylic acids or anhydrides by CÀHa nd CÀCb ond activation have been developed. Furthermore,C7-acylation products can also be generated selectively at alower reaction temperature in the developed system. The key to the high reactivity and regioselectivity of this transformation is the appropriate choice of an indole N-PtBu 2 chelation-assisted group.T his method has many advantages,including easy access and removal of the directing group,the use of cheap and widely available coupling agents,n or equirement of an external ligand or oxidant, ab road substrate scope,h igh efficiency,a nd the formation of asole regioisomer.
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