206766-68-9Relevant academic research and scientific papers
Thermal and hyperbaric addition of N,N- and N,O-binucleophiles on cycloalkylidenic bromo esters
Rulev, Alexandre Y.,Maddaluno, Jacques
, p. 590 - 598 (2007/10/03)
The thermal and high-pressure (11 kbar) induced reaction between 2-bromo-2-(cycloalkylidene)acetates and N,O- and N,N-binucleophiles (such as ethylenediamines or aminoethanols) provides morpholin-2-ones and piperazin-2-ones. Thus, in contrast to simple primary amines, binucleophiles do not form spirocyclic derivatives. The expected Michael addition competes with a cascade reaction consisting of a migration of the double bond followed by the substitution of the newly established allylic halogen and a lactonization (lactamization), and eventually ended by a back-migration of the double bond. Copyright
High pressure vs. thermal activation in the conjugate addition of amines: A new access to spirocyclamines
Rulev, Alexandre Yu.,Maddaluno, Jacques,Ple, Gerard,Plaquevent, Jean-Christophe,Duhamel, Lucette
, p. 1397 - 1401 (2007/10/03)
The reactions of methyl or ethyl 4-tert-butylcyclohexylidene bromoacetates 3-Me or 3-Et with amines afford various products depending on the experimental conditions and the nature of the amine. When the starting ester 3 is treated with benzylamine in refluxing methanol, the ester 5 and the corresponding amide 6 are isolated as the main reaction products. By contrast, the same reaction at room temperature and under high pressure leads to a spiro aziridine derivative 4 in good yield and high stereoselectivity. On the other hand, when ester 3 reacts with secondary amines in refluxing alcohol, the corresponding a-amino β,γ-unsaturated ester 7 is isolated as the sole product of the reaction in good yield. In toluene, the same reaction produces, in addition to the deconjugation-substitution compound 7, the isomeric γ-amino α,β-unsaturated ester 8. Finally, the hetero-Michael type addition of alcohol is the main reaction when substrate 3 is treated with methanol in the presence of a secondary or tertiary amine under high pressure, leading to β-substituted ester 9.
