Regio- and stereoselective synthesis of N-H aziridines by N-N bond reduction of N-quinazolinyl aziridines

Hydroxyl-directed aziridination of the isoprenoid alcohols - geraniol, nero l, and (E,E)-farnesol - with Atkinson's N-acetoxyamino-2-ethyl-4(3H)-quinaz olone reagent (4) afforded N-substituted 2,3-epimino alcohols. Reduction of these and related N-substituted aziridines with metal-ammonia or lithium-n aphthalenide reagents furnished a series of N-H aziridino alcohols (53-74%) including 2,3- and 6,7-epimino geraniols (10 and 13), 2,3-epimino nerol (1 7), (E,E)-2,3-epimino farnesol (23), and syn-2,3-epimino isophorol (20). A less efficient synthesis of the trans-2,3-epimino isoprenoid alcohols 10 an d 23 by irradiation of allylic azidoformates and hydrolysis of the oxazolid inone photoproducts is also reported. These approaches complement known met hods for synthesis of N-H aziridines of isoprenoid polyenes. (C) 1999 Publi shed by Elsevier Science Ltd. All rights reserved.