2009
DOI: 10.1039/b822763b
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Nucleophile-dependent regioselective ring opening of 2-substituted N,N-dibenzylaziridinium ions: bromide versus hydride

Abstract: The ring opening of 2-substituted N,N-dibenzylaziridinium ions by bromide exclusively occurs at the substituted aziridine carbon atom in a stereospecific way, whereas the opposite regioselectivity was observed for hydride-induced ring opening at the unsubstituted position; furthermore, this unprecedented hydride-promoted reactivity was validated by means of Density Functional Theory (DFT) calculations.

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Cited by 37 publications
(18 citation statements)
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“…These were then evaluated as electrophiles for the halide‐induced ring‐opening reactions. Chiral substrates 13a , b were prepared starting from the corresponding commercially available ( R )‐2‐hydroxymethyl‐1‐[( R )‐1‐phenylethyl]aziridine according to literature protocols 5c,5g,5h…”
Section: Resultsmentioning
confidence: 99%
“…These were then evaluated as electrophiles for the halide‐induced ring‐opening reactions. Chiral substrates 13a , b were prepared starting from the corresponding commercially available ( R )‐2‐hydroxymethyl‐1‐[( R )‐1‐phenylethyl]aziridine according to literature protocols 5c,5g,5h…”
Section: Resultsmentioning
confidence: 99%
“…In the current study, transition‐state conformations, including the various spatial position of the ‐OH functionality, of the catalyst with respect to the anhydride have been modeled to highlight the interactions contributing to the stabilization of the oxyanion forming in the transition state and to understand the stereoselectivities with methanol acting as the reaction partner. The distortion/interaction analysis, which has been shown to reveal the origin of selectivities in many organic and organometallic reactions, was employed to evaluate the distortion of the catalyst and its relation to stereoselectivity. Bolm's experimental findings (Scheme ) have been modeled, taking into account the effect of the assistance of solvent molecules that can significantly alter the calculated enantiomeric ratios …”
Section: Introductionmentioning
confidence: 99%
“…In contrast to their activated counterparts, non-activated aziridines have been evaluated to a limited extent up to now, both from a synthetic and a pharmacological point of view. Due to the presence of an electron-donating substituent at nitrogen, the latter aziridines have to be activated toward aziridinium ion intermediates prior to ring opening [18,19,20,21,22,23,24,25,26,27,28,29,30,31]. Within the present work, the scarcely studied subclass of non-activated 1-alkyl-2-(aminomethyl)aziridines [32,33,34,35,36,37,38,39] was employed as a source of substrates for the development of a novel entry toward the biologically relevant 1,2,3-triaminopropane unit through a highly regioselective and microwave-assisted ring opening by diethylamine in acetonitrile.…”
Section: Introductionmentioning
confidence: 99%