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First-Row Transition-Metal Catalyzed Acceptorless Dehydrogenation and Related Reactions: A Personal Account
The Chemical Record ( IF 7.0 ) Pub Date : 2021-08-20 , DOI: 10.1002/tcr.202100165
Murugan Subaramanian 1 , Ganesan Sivakumar 1 , Ekambaram Balaraman 1
Affiliation  

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.

中文翻译:

第一排过渡金属催化无受体脱氢及相关反应:个人账户

避免使用昂贵和贵金属催化剂并避免使用有毒试剂的可持续催化方案的开发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用的原料化学品作为起始材料拓宽了它们在当代研究中的合成应用。特别是,过渡金属催化的醇与各种亲核伙伴的多样化以构建广泛的结构单元是一种强大且非常理想的方法。此外,用非贵金属和毒性较小的金属替代贵金属催化剂进行选择性转化是主要目标之一,并在现代化学中受到了极大的关注。鉴于此,第一排过渡金属催化剂在催化加氢、脱氢及相关反应等各种合成转化中得到广泛应用。在此,我们披露了我们在无受体脱氢反应中的贱金属催化如 Mn、Fe、Co 和 Ni 的最新进展及其在 C-C 和 CN 键形成中的应用通过氢自动转移 (HA) 和无受体脱氢偶联 (ADC) 反应。这些 HA/ADC 协议使用醇作为烷化剂并消除作为副产物的水和/或氢气,代表高原子效率和环境友好的反应。此外,还概述了使用原料醇通过 C-C 和 CN 键形成合成的各种简单到复杂的有机分子。总体而言,该帐户涉及用于可持续化学合成的高效和新型均相和非均相贱金属催化剂的贡献和发展。
更新日期:2021-08-20
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