Synthesis of 1‐Substituted Pyrazolines by Reaction of Donor‐Acceptor Cyclopropanes with 1,5‐Diazabicyclo[3.1.0]hexanes

Abstract

Substituted pyrazolines were obtained by Ni(ClO4)2·6H2O‐catalyzed reaction of 1,5‐diazabicyclo[3.1.0]hexanes with donor‐acceptor cyclopropanes. The mechanism of this reaction includes alkylation of diaziridine nitrogen with Lewis acid‐activated donor‐acceptor cyclopropane followed by hydration of the formed 1,6‐zwitterionic intermediate and oxidation of pyrazolidine with air oxygen. This pathway is realized when starting bicyclic diaziridines have bulky alkyl substituent(s) at the C(6) atom preventing (3+3)‐annulation of two three‐membered rings.

Cobalt-Catalyzed Stereospecific C–N/C–O Bond Formation of Oxiranes with Diaziridines

“…Diaziridines 1b , 1k , 1q , and 1s – t are new, and their characterization data are provided. ( 1a , 1c – f , 1h – i , and 1p ), ( 1g , 1j , and 1m – o ), 1l , and 1r are known and analyzed by comparison with the literature data. To show the purity, 1 H NMR data are given.…”

Recent Advances in the Preparations and Synthetic Applications of Oxaziridines and Diaziridines

“… [100] Later, the protocol was applied for the preparation of substituted pyrazolines 216 from 1,5‐diazabicyclo[3.1.0]hexanes 215 (Scheme 57). [101] …”

“…[100] Later, the protocol was applied for the preparation of substituted pyrazolines 216 from 1,5-diazabicyclo [3.1.0]hexanes 215 (Scheme 57). [101] In 2018, Hoye et al developed a trapping reaction between thermally generated benzyne 220 and diaziridines 218 for the construction of N-arylhydrazones 219 at 85°C (Scheme 58a). [102] The method followed the earlier report by Heine et al with electron deficient alkynes.…”

6,6′-Dimethyl-1,1′,5,5′-tetraaza-6,6′-bi(bicyclo[3.1.0]hexane): synthesis and investigation of molecular structure by quantum-chemical calculations, NMR spectroscopy and X-ray diffraction analysis

“…Diaziridines appeared to be suitable objects for studying of the stereochemistry of the nitrogen atom due to the high stability of the two stereogenic pyramidal nitrogens [21][22][23]. Strained diaziridine ring is inclined to ring-expansion reactions resulting in various ve-to-eight-membered monoand bicyclic heterocyclic structures [24][25][26][27][28][29][30]. These heterocycles possess high enthalpies of formation and though they contain hydrazine fragment are of low toxic compounds.…”