Aziridines saturées et insaturées. Synthèses par réduction de cyclohexénones oximes et études spectroscopiques

Abstract

The reduction of several cyclohexenone oximes using lithium aluminum hydride and sodium dihydrobis-(2-methoxyethoxy)aluminate yields saturated and unsaturated aziridines with a 7-azabicyclo[4.1.0]heptane skeleton and cyclohex-2-ene amines. The use of oximes of E and/or Z configuration demonstrates the regioselectivity of the reduction and allows us to propose reaction schemes explaining the formation of the different types of products.

Regio- and Stereoselectivity of Diethylaluminum Azide Opening of Trisubstituted Epoxides and Conversion of the 3° Azidohydrin Adducts to Isoprenoid Aziridines

“…However, small amounts (≤ 5−10%) of other minor unidentified products isolated might have contained an azide functionality. The structure and trans stereochemistry of 13 were verified by conversion to the known cis -1,2-aziridino limonene by reductive cyclization of the corresponding mesylate (eq 12) …”

Synthesis of 6α,7α- and 6β,7β-aziridinoandrost-4-ene-3,17-diones and related compounds: potential aromatase inhibitors

“…15 h; xi, TMAF, MeCN, N,, room temp., 20 h azido-7a-mesylester 22 (Scheme 5), a well established procedure in which the aziridine ring retains the original configuration of the azidoThe 6P,7P-aziridine 21 was further characterized as the N-acetyl derivative 27 (Scheme 6). As a final confirmation of structure, the aziridine 21 was smoothly deaminated to the known 2 2 androsta-4,6-diene-3,17-dione16 as described above for the 5,6-aziridines.We then turned our attention to the synthesis of the 6a,7aisomer 23 ofcompound 21. Reaction of androsta-4,6-diene-3,17dione 16 with NaN, and 1 mol equiv.…”

A Fit-for-Purpose Synthesis of (R)-2-Methylazepane

“…Alternative synthetic approaches to compound 1 are described in the literature. Besides route A and two reports in which the target was obtained as a minor component of the reaction mixture, three main strategies from commercially available starting materials have been disclosed (Scheme ). Routes B and C , rely on rearrangements of cyclohexanone ( 6 ) and 2-methylcyclohexanone ( 10 ), respectively, while routes D and E proceed through the alkylation of an N-protected ε-caprolactam …”