26119-44-8Relevant academic research and scientific papers
NADH MODELS-19 CYCLOPROPANE RING AS A CHEMICAL PROBE IN THE STUDY OF THE MECHANISM OF HYDROGEN TRANSFER BY 1,4-DIHYDROPYRIDINE DERIVATIVES
Meijer, Louis H. P.,van Niel, Johannes C. G.,Pandit, Upendra K.
, p. 5185 - 5196 (2007/10/02)
N-(Cyclopropylmethylene)phenylamines (1a-c), cyclopropyl 2-pyridyl ketones (5a-c) and ethyl cyclopropylmethylenepyruvate (14) have been subjected to reduction by 1,4-dihydropyridines in the presence of magnesium ions, and by tin hydrides.The reactions with 1,4-dihydropyridines do not involve cleavage of the three-membered ring in the reduction step.The observed acyclic product from 2-pyridyl 2,2-dimethylcyclopropyl ketone (5b) is a consequence of ring cleavage prior to reduction of the carbonyl function.In contrast, reduction of 1a-c and 5a-c by tin hydrides leads to products in which the cyclopropane moiety has undergone ring-opening.These findings support a hydride transfer mechanism for reductions with NADH models.
Conformational Analysis of the Cyclopropylacyl, Oxiranylacyl, and Aziridinylacyl Radicals by Electron Spin Resonance Spectroscopy
Davies, Alwyn G.,Sutcliffe, Roger
, p. 1483 - 1488 (2007/10/02)
A series of ring-substituted cyclopropylacyl, oxiran-2-ylacyl, and aziridin-2-ylacyl radicals have been prepared principally by the reaction of photolytically generated t-butoxyl radicals with the corresponding aldehydes.The e.s.r. spectra show that the cyclopropylacyl ?-radicals exist in s-cis- and s-trans-conformations of approximately equal stability, in which the plane of the acyl group bisects the ring (as it does in the parent aldehyde), and simulation of the spectra through the region of intermediate rates of exchange show that the barrier to rotation is ca. 17.5 kJ*mol-1.The behaviour of the trans-2-ethoxycarbonylcyclopropylacyl and 2,2-dimethylcyclopropylacyl radicals is similar.The oxiranylacyl and trans-3-methyloxiranylacyl radicals exist in the same two conformations with a rather lower barrier, and the N-alkylaziridinylacyl radicals appear to have a lower barrier still.
