Catalytic asymmetric silicon-carbon bond-forming transformations based on Si-H functionalization

Advances in disilylation reactions to access cis/trans-1,2-disilylated and gem-disilylated alkenes

“…6,7 The availability of vacant 3d orbitals enables silicon to readily form five or six-coordinate complexes, resembling the reactivity of some first-row transition metal complexes. 8 Introducing a silyl group into organic molecules will alter their chemical and physical properties, offering unique functionalities to the resulting structures. [9][10][11][12] Carbon/silicon exchange, particularly in drug design, will enhance chemical diversity and modify the physiological and biological properties of bioactive molecules.…”

Silanes as a versatile hydride source for Ni–H catalysis: a promising tool for π-hydro functionalization

“…Indeed, in these reactions, the insertion of a metal-hydride species into π-systems generates an organometallic species in situ , which then reacts with other coupling partners through C–C and C–heteroatom cross-coupling reaction to form new C–C and C–heteroatom bonds. Remarkable advances have been made over the last decade in the research area of π-hydrofunctionalization of sp 2 and sp systems using the most versatile first-row transition metal hydrides such as Cu–H 8 and Ni–H 9 for catalysis (Scheme 1).…”

“…The chemistry of Ni–H species has mainly expanded in the last decade. 9 In addition, Ni–H species are found to be key intermediates for olefin isomerization and polymerization, Heck reaction, hydrogenation, hydrosilylation, and reactions relevant to hydrogen production and utilization. 11 Furthermore, Ni–H species are present in the active sites of Ni-containing enzymes such as methyl-coenzyme M reductase and [NiFe]-hydrogenase.…”

“…The addition of Si–H to the L n Ni complex proceeded via either an oxidative or a non-oxidative pathway. 9 In a typical oxidative pathway, low-valent Ni complexes such as Ni(0) species undergo oxidative addition with the Si–H bond. The non-oxidative process often involves the reaction of a Ni halide or related complex with silanes, where halides can be replaced by hydrides via a ligand substitution process.…”

Substituent-controlled site-selective silylation of 2H-indazoles to access silylated 1H-indazoles and 2H-indazoles under transition metal-free conditions

“…Organosilicon compounds employed as important reagents in organic synthesis are widely present in materials science and medicinal chemistry. 9 Given the excellent transformation of the silyl group, 9 we aim to develop a general strategy for silylating 1 H -indazoles and 2 H -indazoles at the C 3 -position, allowing for controllable modification of these molecules (Scheme 1D). If 1 H -indazoles and 2 H -indazoles can be interconverted by substituent control during the transformation process, this will improve the efficiency of the diversification of indazoles.…”