The chemical transformation of 1 to the corresponding phenyl vinyl ketone (PVK) and the subsequent modification of a thiol containing residue by the PVK.
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posted on 2012-12-28, 01:58 authored by Areej Abuhammad, Elizabeth Fullam, Edward D. Lowe, David Staunton, Akane Kawamura, Isaac M. Westwood, Sanjib Bhakta, Alun Christopher Garner, David L. Wilson, Peter T. Seden, Stephen G. Davies, Angela J. Russell, Elspeth F. Garman, Edith Sim(A) A proposed pathway of the formation of bis-Mannich bases from the rigid cyclic piperidinol. The bis-Mannich base can undergo a β-elimination of the amino group forming a reactive phenyl vinyl ketone (PVK). (B) The PVK reaction with thiols resulted in the addition of a 3-phenyl-3-oxopropyl moiety (POP) (when R1 is H) or a 3-(4-chlorophenyl)-3-oxopropyl moiety (when R1 is Cl). The expected Δm values of the added fragments are +132.07 Da and +166 Da, respectively. The shaded areas highlight the Michael acceptor moiety. Since the PVK binding species is transient, the second order rate constant cannot be determined without major assumptions being made.
