美国加州大学伯克利分校Richmond Sarpong研究小组报道了饱和杂环的光介导的缩环反应。这一研究成果发表在2021年8月12日出版的国际学术期刊《科学》上。

该课题组人员描述了可见光介导的α-酰化饱和杂环的缩环反应。这种非常规的转变与传统的缩环反应正交，挑战了杂环多样化的范式，包括哌啶、吗啡啉、噻烷、四氢吡喃和四氢异喹啉衍生物。这种Norrish II型变体的成功依赖于在特定的化学环境中光反应性酮基团之间的反应性差异。这一策略被应用于药物衍生物、多肽和糖的后期重塑。

据了解，饱和杂环化合物在许多药物和生物活性天然产物中都有发现，在许多药物和农用化合物库中都有丰富的饱和杂环化合物。为了获得新的化学空间和功能，对这些结构的外围功能化已经发展了许多方法。相对而言，很少有方法能够重构其核心框架。

附：英文原文

Title: Photo-mediated ring contraction of saturated heterocycles

Author: Justin Jurczyk, Michaelyn C. Lux, Donovon Adpressa, Sojung F. Kim, Yu-hong Lam, Charles S. Yeung, Richmond Sarpong

Issue&Volume: 2021/08/12

Abstract: Saturated heterocycles are found in numerous therapeutics as well as bioactive natural products and are abundant in many medicinal and agrochemical compound libraries. To access new chemical space and function, many methods for functionalization on the periphery of these structures have been developed. Comparatively fewer methods are known for restructuring their core framework. Herein, we describe a visible light-mediated ring contraction of α-acylated saturated heterocycles. This unconventional transformation is orthogonal to traditional ring contractions, challenging the paradigm for diversification of heterocycles including piperidine, morpholine, thiane, tetrahydropyran, and tetrahydroisoquinoline derivatives. The success of this Norrish Type II variant rests on reactivity differences between photoreactive ketone groups in specific chemical environments. This strategy was applied to late-stage remodeling of pharmaceutical derivatives, peptides, and sugars.

DOI: 10.1126/science.abi7183

Source: https://science.sciencemag.org/content/early/2021/08/11/science.abi7183