Modifying Positional Selectivity in C–H Functionalization Reactions with Nitrogen-Centered Radicals: Generalizable Approaches to 1,6-Hydrogen-Atom Transfer Processes,Synlett

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Modifying Positional Selectivity in C–H Functionalization Reactions with Nitrogen-Centered Radicals: Generalizable Approaches to 1,6-Hydrogen-Atom Transfer Processes
Synlett ( IF 1.7 ) Pub Date : 2019-11-27 , DOI: 10.1055/s-0039-1691501
Melanie A Short ₁ , J Miles Blackburn ₁ , Jennifer L Roizen ₁

Affiliation

Nitrogen-centered radicals are powerful reaction intermediates owing in part to their ability to guide position-selective C(sp3)–H functionalization reactions. Typically, these reactive species dictate the site of functionalization by preferentially engaging in 1,5-hydrogen-atom transfer (1,5-HAT) processes. Broadly relevant approaches to alter the site-selectivity of HAT pathways would be valuable because they could be paired with a variety of tactics to install diverse functional groups. Yet, until recently, there have been no generalizable strategies to modify the position-selectivity observed in these HAT processes. This Synpacts article reviews transformations in which nitrogen-centered radicals preferentially react through 1,6-HAT pathways. Specific attention will be focused on strategies that employ alcohol- and amine-anchored sulfamate esters and sulfamides as templates to achieve otherwise rare γ-selective functionalization reactions. 1 Introduction 2 Transformations that Rely on Structural Constraints or Weakened C–H Bonds to Favor 1,6-HAT Processes 3 Sulfamate Esters Engage Selective 1,6-HAT Processes 4 Expansion to 1,6-HAT Processes with Masked Amine Substrates 5 Conclusions and Outlook

中文翻译：

用氮中心自由基改变 C-H 官能化反应中的位置选择性：1,6-氢原子转移过程的通用方法

以氮为中心的自由基是强大的反应中间体，部分原因在于它们能够引导位置选择性 C(sp3)–H 官能化反应。通常，这些活性物质通过优先参与 1,5-氢原子转移 (1,5-HAT) 过程来决定功能化位点。改变 HAT 途径位点选择性的广泛相关方法将很有价值，因为它们可以与各种策略配合使用来安装不同的功能组。然而，直到最近，还没有通用的策略来修改这些 HAT 过程中观察到的位置选择性。这篇 Synpacts 文章回顾了以氮为中心的自由基优先通过 1,6-HAT 途径进行反应的转化。特别关注的是采用醇和胺锚定的氨基甲酸酯和磺酰胺作为模板来实现罕见的γ选择性官能化反应的策略。1 简介 2 依赖结构约束或减弱的 C-H 键以有利于 1,6-HAT 工艺的转化 3 氨基甲酸酯参与选择性 1,6-HAT 工艺 4 使用掩蔽胺底物扩展到 1,6-HAT 工艺 5 结论和外表

更新日期：2019-11-27

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