The role of the ester group in determining the regiochemistry of selected β-amino and β-ammonio radical cyclisations: generation of 1-azabicyclo[3.2.1]octyl- and -[2.2.2]octyl systems

Author(s):  
Ernest W. Della ◽  
Paul A. Smith
2005 ◽  
Vol 16 (23) ◽  
pp. 3853-3857 ◽  
Author(s):  
Mathieu Pizzonero ◽  
Frédéric Hendra ◽  
Sandrine Delarue-Cochin ◽  
Marie-Elise Tran Huu-Dau ◽  
Françoise Dumas ◽  
...  

2021 ◽  
Author(s):  
Veejendra Yadav ◽  
Dasari L V K Prasad ◽  
Arpita Yadav ◽  
Maddali L N Rao

<p>The predominant transformations of 4-methyl- and 4-phenyl-1,3,3-<i>tris</i>-carbethoxycyclobutenes to s-<i>trans</i>,<i>trans</i>-1,1,3-<i>tris</i>-carbethoxy-4-methyl- and s-<i>trans</i>,<i>trans</i>-1,1,3-<i>tris</i>-carbethoxy-4-phenyl-1,3-butadienes, respectively, are discussed to proceed through pathways entailing heterolytic cleavage of the s<sub>C3C4</sub> bond rather than the usual conrotatory ring opening following the rules of torquoselectivity. The adventitious or in situ generated halogen acid from CDCl<sub>3</sub> catalyzes the reaction by protonation of the geminal ester group to weaken s<sub>C3C4</sub> bond and allow its S<sub>N</sub>2 cleavage by chloride ion. This is followed by cisoid<b>→</b>transoid isomerization and loss of the elements of halogen acid to form the products. In the Lewis acid-catalyzed reaction of 4-phenyl-1,3,3-<i>tris</i>-carbethoxycyclobutene in CH<sub>2</sub>Cl<sub>2</sub>, coordination of Lewis acid with the geminal ester group is followed by heterolytic cleavage of the s<sub>C3C4</sub> bond. The resultant species subsequently undergoes cisoid<b>→</b>transoid isomerization before losing the Lewis acid to form the products.<br></p>


1981 ◽  
Vol 59 (12) ◽  
pp. 1239-1244 ◽  
Author(s):  
James R. P. Godin ◽  
Gerard Llanos ◽  
Keith Vaughan ◽  
Kenneth W. Renton

A series of dimethyltriazenes (Ar∙N=N∙NMe2), monomethyltriazenes (Ar∙N=N∙NH∙Me), and triazene carbinolamines (Ar∙N=N∙NMe∙CH2OH) have been studied for their inhibitory effects on the enzyme, hog liver esterase (EC 3.1.1.1). p-Nitrophenyl acetate was used as the model substrate and the rate of hydrolysis was followed spectrophotometrically at 400 nm, the absorption maximum of the p-nitrophenylate ion. Only triazenes with an ester group in the aryl moiety exhibited significant inhibition. Preincubation of the enzyme with the monomethyltriazene (MeO2C∙C6H4∙N=N∙NHMe) or the methyloltriazene (MeO2C∙C6H4∙N=N∙NMe∙CH2OH) gave enhanced inhibition, which was not observed when the dimethyltriazene (MeO2C∙C6H4∙N=N∙NMe2) was preincubated with the enzyme. Inhibition of enzyme activity by the monomethyltriazene was shown to be essentially irreversible, whereas the model substrates, methyl benzoate and methyl p-aminobenzoate, gave reversible inhibition in the same assay. The inhibition by the N-methyloltriazene was only partially reversible. The results are discussed with relevance to the role of the monomethyltriazenes and N-methyloltriazenes as possible transportable metabolites of the antitumour dimethyltriazenes.


JAMA ◽  
1966 ◽  
Vol 195 (12) ◽  
pp. 1005-1009 ◽  
Author(s):  
D. J. Fernbach
Keyword(s):  

JAMA ◽  
1966 ◽  
Vol 195 (3) ◽  
pp. 167-172 ◽  
Author(s):  
T. E. Van Metre

2018 ◽  
Vol 41 ◽  
Author(s):  
Winnifred R. Louis ◽  
Craig McGarty ◽  
Emma F. Thomas ◽  
Catherine E. Amiot ◽  
Fathali M. Moghaddam

AbstractWhitehouse adapts insights from evolutionary anthropology to interpret extreme self-sacrifice through the concept of identity fusion. The model neglects the role of normative systems in shaping behaviors, especially in relation to violent extremism. In peaceful groups, increasing fusion will actually decrease extremism. Groups collectively appraise threats and opportunities, actively debate action options, and rarely choose violence toward self or others.


2018 ◽  
Vol 41 ◽  
Author(s):  
Kevin Arceneaux

AbstractIntuitions guide decision-making, and looking to the evolutionary history of humans illuminates why some behavioral responses are more intuitive than others. Yet a place remains for cognitive processes to second-guess intuitive responses – that is, to be reflective – and individual differences abound in automatic, intuitive processing as well.


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