Developing a Catalytic Strategy to Address Regiocontrol in Radical Reactions of Aromatic Heterocycles

制定催化策略来解决芳香杂环自由基反应中的区域控制问题

• 批准号: 1800778
• 金额: --
• 依托单位: University of Cambridge
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2016
• 资助国家: 英国
• 起止时间: 2016 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-1800778
• 关键词: Developing; Catalytic; Strategy; Address; Regiocontrol

Construction of basic heteroarenes with varied substitution patterns is of great importance, but direct transformation of heterocyclic C-H bonds is a major challenge, often due to incompatibility with metal catalysts. Minisci-type additions are radical addition processes in which a basic heterocycle is protonated with a concomitant lowering of its LUMO, before attack by 'nucleophilic' radicals. This is a deceptively simple method with no catalyst required. The problem that has held back its widespread use is a lack of regioselectivity on heterocycles such as pyridines and quinolines due to insufficiently different LUMO coefficients of the C2 and C4 positions. We will develop a catalytic approach to Minisci additions that will allow us to control regioselectivity between C2 and C4. We anticipate that successful realisation of this strategy will allow the wealth of radical chemistry to be applied to valuable basic heterocycles with new-found regiocontrol.

具有不同取代模式的基本杂芳烃的构建是非常重要的，但是杂环C-H键的直接转化是一个主要挑战，通常是由于与金属催化剂不相容。迷你型加成是自由基加成过程，其中碱性杂环在被“亲核”自由基攻击之前被质子化，伴随着其LUMO的降低。这是一种看似简单的方法，不需要催化剂。阻碍其广泛应用的问题是由于C2和C4位置的LUMO系数差异不够大，对杂环如吡啶和喹啉缺乏区域选择性。我们将开发一种催化方法Minisci加成，使我们能够控制C2和C4之间的区域选择性。我们预计，这一策略的成功实现将使丰富的自由基化学能够应用于具有新发现的区域控制的有价值的基本杂环。

项目成果

Hydrogen Atom Transfer Driven Enantioselective Minisci Reaction of Alcohols.

• DOI: 10.1002/anie.202200266
• 发表时间: 2022-06-20
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Colgan, Avene C.;Proctor, Rupert S. J.;Gibson, David C.;Chuentragool, Padon;Lahdenpera, Antti S. K.;Ermanis, Kristaps;Phipps, Robert J.
• 通讯作者: Phipps, Robert J.

Hydrogen Atom Transfer-Driven Enantioselective Minisci Reaction of Amides.

• DOI: 10.1021/jacs.1c01556
• 发表时间: 2021-04-07
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Proctor RSJ;Chuentragool P;Colgan AC;Phipps RJ
• 通讯作者: Phipps RJ