Abstract:
An overview of the development of compounds with heavier low‐valent group 14 elements (known as tetrylenes) as single component catalyst for organic transformation has been provided. Compounds with heavier group 14 elements possess stereochemically active lone pairs and energetically accessible π‐antibonding orbitals, thereby resembling the electronic configuration of transition‐metal compounds. Such compounds with low‐valent group 14 elements has been known for small molecule activation since Power's report of dihydrogen activation by a digermyne, but their utilization in catalysis remained as a “Holy Grail” in main group chemistry. In recent years, numerous methodologies have been discovered epitomizing the use of Si(II), Ge(II) and Sn(II) compounds as single site catalysts for hydroboration of aldehydes, ketones, pyridines, cyanosilylation of aldehydes and ketones, N‐formylations aromatic amines, dehydrocoupling reactions. This mini‐review highlights these significant developments with an emphasis on the mechanistic investigation.