Sen Nilanjana, Khan Shabana
Department of Chemistry, Indian Institute of Science Education and Research (IISER), Pune, Dr. Homi Bhabha Road, Pashan, Pune, 411008, India.
Chem Asian J. 2021 Apr 1;16(7):705-719. doi: 10.1002/asia.202100038. Epub 2021 Mar 1.
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.
本文综述了以较重的低价14族元素化合物（即“特瑞烯”）作为单组分催化剂用于有机转化的发展概况。含有较重14族元素的化合物具有立体化学活性孤对电子和能量上可及的π反键轨道，因此类似于过渡金属化合物的电子构型。自从鲍尔报道二锗烯对氢气的活化以来，这类低价14族元素化合物就已用于小分子活化，但它们在催化中的应用在主族化学领域仍然是一个“圣杯”。近年来，人们发现了许多方法，这些方法体现了硅（II）、锗（II）和锡（II）化合物作为单中心催化剂用于醛、酮、吡啶的硼氢化反应、醛和酮的氰基硅烷化反应、芳香胺的N-甲酰化反应以及脱氢偶联反应。这篇综述强调了这些重要进展，并着重于机理研究。
