ABSTRACT
This review presents a brief discussion on the numerous synthetic techniques used to prepare metal nanoparticles supported on various two-dimensional (2D) materials. Special emphasis has been given to graphene and other 2D analogues such as g-C3N4, h-BN, MoS2, WS2 etc. supported metal nanoparticles. In addition to these, this review outlines the applications of the developed metal nanoparticles–2D composite materials for catalytic coupling reactions, which have recently emerged as a promising strategy in carbon–heteroatom or carbon–carbon bond formation. The effect of size and morphology of metal nanoparticles–2D composite materials on their catalytic performance toward different coupling reactions such as Suzuki, Heck, Sonogashira, etc. have been discussed in detail.
Implemented with the highly efficient concept of Dynamic Kinetic Resolution (DKR), dynamic covalent chemistry can be a useful strategy for the synthesis of enantioenriched compounds. This gives rise to dynamic covalent kinetic resolution (DCKR), a subset of DKR that over the last decades has emerged as increasingly fruitful, with many applications in asymmetric synthesis and catalysis. All DKR protocols are composed of two important parts: substrate racemization and asymmetric transformation, which can lead to yields of >50% with good enantiomeric excesses (ee) of the products. In DCKR systems, by utilizing reversible covalent reactions as the racemization strategy, the substrate enantiomers can be easily interconverted without the presence of any racemase or transition metal catalyst. Enzymes or other chiral catalysts can then be adopted for the resolution step, leading to products with high enantiopurities. This tutorial review focuses on the development of DCKR systems, based on different reversible reactions, and their applications in asymmetric synthesis.
Cyano group as a versatile functionalized intermediate has been explored for several decades, as it readily transfers to many useful functionalization groups such as amine, amide, acid, etc., which make it possess high popularization and use value in organic synthesis. Reactions involved with element-cyano bond cleavage can provide not only a new cyano group but also a freshly functionalized skeleton in one-pot, consequently making it of high importance. The highlights reviewed herein include H-CN, Si-CN, C-CN, B-CN, Sn-CN, Ge-CN, S-CN, Halo-CN, N-CN, and O-CN bonds cleavages and will summarize progress in such an important research area. This review article will focus on transition metal catalyzed reactions involving element-cyano bond activation.