Subaramanian Murugan, Sivakumar Ganesan, Balaraman Ekambaram
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati, Tirupati, 517507, India.
Chem Rec. 2021 Dec;21(12):3839-3871. doi: 10.1002/tcr.202100165. Epub 2021 Aug 20.
The development of sustainable catalytic protocols that circumvent the use of expensive and precious metal catalysts and avoid toxic reagents plays a crucial role in organic synthesis. Indeed, the direct employment of simple and abundantly available feedstock chemicals as the starting materials broadens their synthetic application in contemporary research. In particular, the transition metal-catalyzed diversification of alcohols with various nucleophilic partners to construct a wide range of building blocks is a powerful and highly desirable methodology. Moreover, the replacement of precious metal catalysts by non-precious and less toxic metals for selective transformations is one of the main goals and has been paid significant attention to in modern chemistry. In view of this, the first-row transition metal catalysts find extensive applications in various synthetic transformations such as catalytic hydrogenation, dehydrogenation, and related reactions. Herein, we have disclosed our recent developments on the base-metal catalysis such as Mn, Fe, Co, and Ni for the acceptorless dehydrogenation reactions and its application in the C-C and C-N bond formation via hydrogen auto-transfer (HA) and acceptorless dehydrogenation coupling (ADC) reactions. These HA/ADC protocols employ alcohol as alkylating agents and eliminate water and/or hydrogen gas as by-products, representing highly atom-efficient and environmentally benign reactions. Furthermore, diverse simple to complex organic molecules synthesis by C-C and C-N bond formation using feedstock alcohols are also overviewed. Overall, this account deals with the contribution and development of efficient and novel homogeneous as well as heterogeneous base-metal catalysts for sustainable chemical synthesis.
开发可持续的催化方案以避免使用昂贵的贵金属催化剂并避免使用有毒试剂，在有机合成中起着至关重要的作用。事实上，直接使用简单且大量可得的原料化学品作为起始原料，拓宽了它们在当代研究中的合成应用。特别是，过渡金属催化醇与各种亲核试剂发生多样化反应以构建各种结构单元，是一种强大且非常理想的方法。此外，用非贵金属和低毒金属替代贵金属催化剂进行选择性转化是主要目标之一，并且在现代化学中受到了广泛关注。有鉴于此，第一行过渡金属催化剂在各种合成转化中得到了广泛应用，如催化氢化、脱氢及相关反应。在此，我们披露了我们最近在贱金属催化方面的进展，例如锰、铁、钴和镍用于无受体脱氢反应及其在通过氢自动转移（HA）和无受体脱氢偶联（ADC）反应形成碳 - 碳和碳 - 氮键中的应用。这些HA/ADC方案使用醇作为烷基化剂，并消除水和/或氢气作为副产物，代表了高原子经济性和环境友好的反应。此外，还概述了使用原料醇通过碳 - 碳和碳 - 氮键形成合成从简单到复杂的各种有机分子的情况。总体而言，本综述论述了高效、新颖的均相和非均相贱金属催化剂对可持续化学合成的贡献与发展。
