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脱金属卟啉光催化 C(sp 2 )-H 键氮丙啶化反应。

Decatungstate-photocatalysed C(sp)-H azidation.

机构信息

Department of Chemistry, Rice University, 6500 Main St, Houston, TX, USA.

出版信息

Chem Commun (Camb). 2022 Apr 14;58(31):4869-4872. doi: 10.1039/d2cc00425a.

Abstract

C-H Azidation is an increasingly important tool for bioconjugation, materials chemistry, and the synthesis of nitrogen-containing natural products. While several approaches have been developed, these often require exotic and energetic reagents, expensive photocatalysts, or both. Here we report a simple and general C-H azidation reaction using earth-abundant tetra--butylammonium decatungstate as a photocatalyst and commercial -acetamidobenzenesulfonyl azide (-ABSA) as the azide source. This system can azidate a variety of unactivated C(sp)-H bonds in moderate to good yields and excellent turnover numbers. Preliminary mechanistic experiments implicate a radical mechanism proceeding photo-hydrogen atom transfer (photo-HAT).

摘要

C-H 叠氮化物是生物偶联、材料化学和含氮天然产物合成中越来越重要的工具。虽然已经开发了几种方法,但这些方法通常需要奇特且高能的试剂、昂贵的光催化剂或两者兼而有之。在这里,我们报告了一种使用丰富的四丁基铵十钨酸盐作为光催化剂和商业 - 乙酰氨基苯磺酰叠氮化物(-ABSA)作为叠氮化物源的简单而通用的 C-H 叠氮化反应。该体系可以中等至良好的收率和优异的周转数将各种未活化的 C(sp)-H 键叠氮化。初步的机理实验表明该反应是一种自由基机理,涉及光氢原子转移(photo-HAT)。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ad38/9020444/c1ffcd435425/nihms-1793994-f0001.jpg

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