桥连 N-取代氮杂臭氧化物的级联组装：氮源亲核性的反直觉作用

Cascade Assembly of Bridged N-Substituted Azaozonides: The Counterintuitive Role of Nitrogen Source Nucleophilicity.

作者信息

Yaremenko Ivan A, Belyakova Yulia Yu, Radulov Peter S, Novikov Roman A, Medvedev Michael G, Krivoshchapov Nikolai V, Alabugin Igor V, Terent'ev Alexander O

机构信息

N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prospect, Moscow 119991, Russian Federation.

Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.

出版信息

Org Lett. 2022 Sep 16;24(36):6582-6587. doi: 10.1021/acs.orglett.2c02551. Epub 2022 Sep 7.

DOI:10.1021/acs.orglett.2c02551

PMID:36070396

Abstract

Counterintuitively, the low basicity of the NH group in hydrazides makes them preferred nucleophiles for the synthesis of the N-substituted azaozonides in acid-catalyzed three-component condensation with 1,5-diketones and HO. In the case of more basic N sources, e.g., hydrazine and primary amines, such condensation does not occur under these reaction conditions. The method can be applied to a wide range of hydrazides and affords the target bicyclic azaozonides in 27-86% yields.

摘要

与直觉相反，酰肼中NH基团的低碱性使其成为在酸催化下与1,5-二酮和HO进行三组分缩合反应合成N-取代氮杂臭氧化物时更优的亲核试剂。对于碱性更强的氮源，如肼和伯胺，在这些反应条件下不会发生这种缩合反应。该方法可应用于多种酰肼，并以27%至86%的产率得到目标双环氮杂臭氧化物。