Duke University, Department of Chemistry, Box 90346, Durham, NC, 27708-0354, USA.
Angew Chem Int Ed Engl. 2018 Jan 2;57(1):296-299. doi: 10.1002/anie.201710322. Epub 2017 Dec 7.
Masked alcohols are particularly appealing as directing groups because of the ubiquity of hydroxy groups in organic small molecules. Herein, we disclose a general strategy for aliphatic γ-C(sp )-H functionalization guided by a masked alcohol. Specifically, we determine that sulfamate ester derived nitrogen-centered radicals mediate 1,6-hydrogen-atom transfer (HAT) processes to guide γ-C(sp )-H chlorination. This reaction proceeds through a light-initiated radical chain-propagation process and is capable of installing chlorine atoms at primary, secondary, and tertiary centers.
掩蔽醇作为导向基团特别有吸引力，因为羟基在有机小分子中普遍存在。在此，我们披露了一种由掩蔽醇引导的脂肪族γ-C(sp 3 )-H 官能化的通用策略。具体而言，我们确定磺酰胺酯衍生的氮中心自由基介导 1,6-氢原子转移 (HAT) 过程来引导γ-C(sp 3 )-H 氯化。该反应通过光引发的自由基链传播过程进行，能够在伯、仲和叔中心上安装氯原子。
