Rare example of nucleophilic substitution at vinylic carbon with inversion: Mechanism of methyleneaziridine formation by sodium amide induced ring closure revisited

Journal of the American Chemical Society

Volumn 126, Issue 22, 2004, Pages 6868-6869

  Shiers, Jason J ^a   Shipman, Michael ^a   Hayes, Jerome F ^b   Slawin, Alexandra M Z ^c  

^a UNIVERSITY OF WARWICK   (United Kingdom)

^b GLAXOSMITHKLINE   (United Kingdom)

^c UNIVERSITY OF ST ANDREWS   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

2 BROMOALLYLAMINE; 2 BROMOBUT 2 ENYLAMINE; 2 ETHYLENEAZIRIDINE; ALPHA METHYLBENZYL DERIVATIVE; AMIDE; AMMONIA; ANION; AZIRIDINE DERIVATIVE; BENZYLAMINE; CARBANION; CARBON; HETEROCYCLIC COMPOUND; METHANESULFONYL CHLORIDE; METHYLENEAZIRIDINE; NITROGEN; SODIUM AMIDE; SOLVENT; TRIFLUOROMETHANESULFONIC ACID VINYL ESTER; TRITIUM; UNCLASSIFIED DRUG; VINYL CHLORIDE; VINYL DERIVATIVE;

ALKYLATION; ARTICLE; BIOMOLECULAR ELECTRONICS; CHEMICAL REACTION; CHIRALITY; CRYSTALLOGRAPHY; DERIVATIZATION; DIASTEREOISOMER; GEOMETRY; ISOMER; LITHIATION; NUCLEAR OVERHAUSER EFFECT; REACTION ANALYSIS; RING CLOSING METATHESIS; STEREOCHEMISTRY; X RAY CRYSTALLOGRAPHY; X RAY DIFFRACTION;

EID: 3042816129     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0482684     Document Type: Article

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25. 3.
26. Substrates (E)- and (Z)-2a,b contained traces of the double bond isomer (≤8%). This was relayed into the aziridines which also contained a small quantity of the stereoisomer (≤9%). See Supporting Information.
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29. 1H NMR spectroscopy and is the average of three experimental runs.
30. 3. In our experience, the activity of commercial material is far inferior and often necessitates the use of a large excess of reagent. Second, 6 used in the experiment was contaminated with 7% of the corresponding alkyne which would have consumed a significant proportion of the added base.