Three decades of unveiling the complex chemistry of C-nitroso species with computational chemistry,Organic Chemistry Frontiers

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Three decades of unveiling the complex chemistry of C-nitroso species with computational chemistry
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2021-11-09 , DOI: 10.1039/d1qo01415c
Pauline Bianchi ₁ , Jean-Christophe M. Monbaliu ₁

Affiliation

C-Nitroso species are characterized by a unique nitrogen–oxygen combination located next to a carbon backbone, which confers them a unique ambiphilic and high reactivity towards nucleophilic, electrophilic but also radical species. Although this ambivalence can be seen as a strong asset for developing versatile synthetic aminohydroxylation and/or hydroxylamination processes mainly through nitroso Diels–Alder, nitroso ene, and nitrosoaldol reactions, it also contributes to complex optimization and rationalization arising from the many competitive pathways, that is, the occurrence of regioisomers and stereoisomers, as well as dimerization and tautomerization side-reactions. Complex reactivity profiles are usually seen by synthetic organic chemists as major hurdles to overcome, despite the armada of analytical and purification methods available to them, and hence to achieve selective and exploitable developments of such reactions. The rise of computational chemistry and resources has certainly changed their perspectives, since it provides a very different angle to gather insights on intrinsic properties, reactivity, and mechanisms. In silico chemistry also provides a robust alternative to time and resource-consuming synthetic work and can therefore contribute to alleviate wasteful preparations by guiding the chemist toward the best combination of reagents to achieve high selectivity and yield. The synergistic combination of synthetic organic chemistry and computational chemistry, within the specific context of the complex chemistry of C-nitroso species, is discussed in this work. This review aims at giving an overview of the molecular and chemical properties obtained through computational chemistry as an enabling support for the rationalization and optimization of reactions relying on ambiphilic C-nitroso species over the 3 last decades. It provides clear, concise, and illustrated guidelines for the synthetic chemist in search of inspiration through computations.

中文翻译：

用计算化学揭示 C-亚硝基物种的复杂化学的三个十年

C-亚硝基物种的特征在于位于碳骨架旁边的独特氮-氧组合，这赋予它们独特的两亲性和对亲核、亲电以及自由基物种的高反应性。尽管这种矛盾性可以被视为主要通过亚硝基 Diels-Alder、亚硝基烯和亚硝基醛醇反应开发多功能合成氨基羟基化和/或羟胺化过程的强大资产，但它也有助于由许多竞争途径引起的复杂优化和合理化，即即，区域异构体和立体异构体的出现，以及二聚化和互变异构化副反应。合成有机化学家通常将复杂的反应性曲线视为需要克服的主要障碍，尽管他们可以使用分析和纯化方法的舰队，从而实现此类反应的选择性和可利用的发展。计算化学和资源的兴起无疑改变了他们的观点，因为它提供了一个非常不同的角度来收集对内在特性、反应性和机制的见解。计算机化学还为耗费时间和资源的合成工作提供了可靠的替代方案，因此可以通过指导化学家采用最佳试剂组合来实现高选择性和高产率，从而有助于减少浪费的制备。在这项工作中讨论了合成有机化学和计算化学的协同组合，在C-亚硝基物种复杂化学的特定背景下。本综述旨在概述通过计算化学获得的分子和化学性质，作为对依赖于两亲性C的反应合理化和优化的有力支持。- 过去 3 年的亚硝基物种。它为合成化学家通过计算寻找灵感提供了清晰、简洁和图解的指南。

更新日期：2021-12-01

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