Recent advances in catalytic pnictogen bond forming reactions via dehydrocoupling and hydrofunctionalization
Recent advances in catalytic pnictogen bond forming reactions via dehydrocoupling and hydrofunctionalization
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通过脱氢偶联和氢功能化催化磷元素成键反应的最新进展
DOI：
10.1039/d2cc06143k
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发表时间：
2023
影响因子：
4.9
通讯作者：
Waterman, Rory
中科院分区：
文献类型：
--
作者：
Reuter, Matthew B.;Seth, Dennis M.;Javier-Jiménez, Diego R.;Finfer, Emma J.;Beretta, Evan A.;Waterman, Rory
对15族元素间的几种催化反应进行了研究。氮族元素化学之间的联系有时可能具有挑战性，但金属-氮族元素反应性方面是关键。连接反应性来自金属催化的转化，如脱氢偶联和氢官能化。从E-N异脱氢偶联的基本机理的见解为这些反应的高活性催化剂的开发提供了信息。金属-氨基亲核性通常是这种反应性的核心，其不同于膦和胂脱氢偶联。亲核性与最早对氢化膦化催化的理解有关，但最近的催化剂通过光解利用增强的插入活性。这种不稳定性延伸到氢化砷化，其也可能具有比预期更多的金属砷基亲核性。然而，金属催化的砷化烯化学多年来预示了相关的膦化烯化学。这项研究显示了个体发现和理解对利用这些元素之间的新进展产生更大影响的潜力，它还表明，较重元素的化学可能对较轻元素的可能性产生更大的影响。
An examination of several catalytic reactions among the group 15 elements is presented. The connections between the chemistry of the pnictogens can sometimes be challenging, but aspects of metal–pnictogen reactivity are the key. The connecting reactivity comes from metal-catalyzed transformations such as dehydrocoupling and hydrofunctionalization. Pivotal mechanistic insights from E–N heterodehydrocoupling have informed the development of highly active catalysts for these reactions. Metal–amido nucleophilicity is often at the core of this reactivity, which diverges from phosphine and arsine dehydrocoupling. Nucleophilicity connects to the earliest understanding of hydrophosphination catalysis, but more recent catalysts are leveraging enhanced insertion activity through photolysis. This photocatalysis extends to hydroarsination, which may also have more metal–arsenido nucleophilicity than anticipated. However, metal-catalyzed arsinidene chemistry foreshadowed related phosphinidene chemistry by years. This examination shows the potential for greater influence of individual discoveries and understanding to leverage new advances between these elements, and it also suggests that the chemistry of heavier elements may have more influence on what is possible with lighter elements.