Synthesis and enantioselective rearrangement of meso-aziridino cyclohexene oxides

Tetrahedron Letters

Volumn 40, Issue 48, 1999, Pages 8427-8430

  O'Brien, Peter ^a   Pilgram, Christopher D ^a  

^a UNIVERSITY OF YORK   (United Kingdom)

Author keywords

Allylic alcohols; Aziridines; Epoxides; Rearrangement

Indexed keywords

ALLYL ALCOHOL; AZIRIDINE; BASE; CYCLOHEXANE OXIDE; EPOXIDE;

ARTICLE; CHEMICAL MODIFICATION; CHIRALITY; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0033607620     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01741-4     Document Type: Article

References (30)

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10. The reaction of N-tosyl or N-diphenylphosphinoyl-7-azabicyclo[4.1.0]heptane with lithium amides at room temperature for 48 h did not produce any allylic amines: O'Brien, P.; Pilgram, C. D. unpublished results.
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26. Working up the rearrangement of aziridino epoxide cis-2 with dilute hydrochloric acid (our usual procedure) did not give allylic alcohol 3; instead, an unknown product was isolated as the sole product from this reaction. However, quenching the reaction with aqueous ammonium chloride afforded good yields of the desired allylic alcohol.
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30. 1H NMR spectrum of its diastereomeric Mosher's esters. Simple acylation of this gave allylic acetate 9 of known absolute stereochemistry (stereochemistry of major enantiomer shown below). Allylic alcohol 3 was assigned the stereochemistry depicted below since a compound enriched in ent-9 (as shown by the sign of the optical rotation) was generated by the Mitsunobu reaction of 3 with acetic acid. Thus, both of the rearrangement reactions led to the expected (see Refs. 5-7 and references cited therein) (S) stereochemistry at the allylic hydroxyl group (1S). (equation presented)