BF₃·OEt₂/TMSN₃ Mediated Regioselective Azidolysis of Vinylaziridines

Abstract

An easy and general azidolysis of vinylepoxides mediated by BF₃·OEt₂ and TMSN₃ recently reported by our group has been extended to vinylaziridines. The reaction affords unsaturated azido derivatives with complete stereoselectivity and regioselectivity, when in the presence of electron-poor olefins, regardless of the size of substituents on the heterocyclic ring.

Key words

vinylepoxides - vinylaziridines - azidolysis - azido alcohols - azido amines

• References

• 1 Current position: Dr. Ilaria Tirotta, Post Doctoral Researcher, Ludwig Maximilians-Universität München, Department Chemie & Biochemie, Butenandtstrasse 5-13, Haus F, 81377 München, Germany. Fax: [phone]
• 2a Olofsson B, Somfai P In Aziridines and Epoxides in Organic Synthesis . Yudin AK. Wiley-VCH; Weinheim: 2006: 315-443
• 2b Padwa A, Murphree SS. ARKIVOC 2006; (iii): 6
• 3 Ko SY, Lee AW. M, Masamune S, Reed L, Hi A, Sharpless KB, Walker FJ. Tetrahedron 1990; 46: 245
• 4 Righi G, Salvati Manni L, Bovicelli P, Pelagalli R. Tetrahedron Lett. 2011; 52: 3895
• 5a Rodrigues JA. R, Milagre H, Milagre CD. F, Moran PJ. S. Tetrahedron: Asymmetry 2005; 16: 3099

For a review on this topic, see:
• 5b Ghorai MK, Kumar A, Tiwari DP. J. Org. Chem. 2010; 75: 137
• 5c Padwa A In Comprehensive Heterocyclic Chemistry III . Vol. 1. Padwa A. Elsevier; Oxford: 2008. Chap. 1.01
• 5d Fontana F, Chen CC, Aggarwal VK. Org. Lett. 2011; 13: 3454 ; and references cited therein
• 6a Miyashita M, Mizutani T, Tadano G, Iwata Y, Miyazawa M, Tanino K. Angew. Chem. Int. Ed. 2005; 44: 5094
• 6b Marié JC, Courillon C, Malacria M. ARKIVOC 2007; (v): 277
• 7 Solladié-Cavallo A, Lupattelli P, Bonini C. J. Org. Chem. 2005; 70: 1605
• 8 For the purpose of this work, it is not mandatory to have optically active compounds; all the molecules are intended as racemates and the reported stereochemistry is only relative.
• 9 For the substrates with R = cyclohexyl, the appropriate alcohol 1b is not commercially available and was synthesised from cyclohexanecarboxaldehyde. A Horner–Emmons reaction, followed by reduction of the resulting ester using DIBAL-H, led to alcohol 1b in an overall yield of 97%.
• 10a Antonioletti R, Bonadies F, Ciammaichella A, Viglianti A. Tetrahedron 2008; 64: 4644
• 10b Lattanzi A, Orelli LR, Barone P, Massa A, Iannece C, Scettri A. Tetrahedron Lett. 2003; 44: 1333
• 10c Bonadies F, Scettri A, Di Campli C. Tetrahedron Lett. 1996; 37: 1899
• 11 Legters J, Thijs L, Zwanemburg B. Recl. Trav. Chim. Pays-Bas 1992; 111: 1
• 12 Gao Y, Klunder JM, Hanson RM, Masamune H, Ko SY, Sharpless KB. J. Am. Chem. Soc. 1987; 109: 5765
• 13 De Mico A, Margarita R, Parlanti L, Vescovi A, Piancatelli G. J. Org. Chem. 1997; 62: 6974
• 14 Righi G, Chionne A, Bonini C. Eur. J. Org. Chem. 2000; 3127
• 15 Righi G, Bovicelli P, Barontini M, Tirotta I. Green Chem. 2012; 14: 495
• 16 Righi G, Mandic’ E, Naponiello GC. M, Bovicelli P, Tirotta I. Tetrahedron 2012; 68: 2984