Inverse kinetic isotope effect in Magtrieve™ mediated oxidation or deoximation of benzaldoxime: mechanistic implication
作者： Sandeep Bhosale , Dnyaneshwar P. Sonune , Uppuleti Viplava Prasad , Debnath Bhuniya
DOI: 10.1016/J.TETLET.2012.01.111
关键词: Kinetics 、 Deuterium 、 Stereochemistry 、 Benzaldehyde 、 Cycloaddition 、 Chemistry 、 Substrate (chemistry) 、 Medicinal chemistry 、 Rate-determining step 、 Inverse 、 Kinetic isotope effect
摘要: Abstract Magtrieve™ (CrO 2 ) mediated reactions with benzaldoxime ( 1a and its deuterium congener d - led to the observation of inverse kinetic isotope effect (i-DKIE) for substrate’s oxidation (Eq. 1a) as well deoximation 2a) process. Disappearance starting material formation products—1,3-dipolar cycloaddition product 4a benzaldehyde 3a )—followed a typical 1st-order kinetics. The observed k D / H values, in range 2–4, suggest strong secondary which was further evidenced by fact that d-labeling retained . Therefore, i-SDKIE supports our original hypothesis aldoxime (with sp -C) interacts CrO rate determining step form tetrahedral (now 3 structure, possibly like 6 , may act common intermediate both pathways.
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