Synthesis of Heterocycles Containing an N-O Bond by Ring-Closing Meta­thesis of Dienes Tethered by Hydroxylamine

Abstract

The dienes tethered by hydroxylamine were efficiently cyclized into 6- to 10-membered heterocycles containing an N-O bond by catalytic ring-closing metathesis.

Key words

cyclizations - heterocycles - metathesis - ring closure - ruthenium

References

• For reviews on the synthesis of 1,2-oxazines by Diels-Alder reactions, see:
• 1a Streith J. Defoin A. Synlett  1996,  198 
• 1b Denmark SE. Thorarensen A. Chem. Rev.  1996,  96:  137 
• 1c Vogt PF. Miller MJ. Tetrahedron  1998,  54:  1317 
• 2a Peglow T. Blechert S. Streckhan E. Chem. Commun.  1999,  433 
• 2b Schade W. Reissig H.-U. Synlett  1999,  632 
• 2c Shin I. Lee M.-R. Lee J. Jung M. Lee W. Yoon J. J. Org. Chem.  2000,  65:  7667 
• 2d Koenig SG. Leonard KA. Lowe RS. Austin DJ. Tetrahedron Lett.  2000,  41:  9393 
• 2e Ishikawa T. Senzaki M. Kadoya R. Morimoto T. Miyake N. Izawa M. Saito S. J. Am. Chem. Soc.  2001,  123:  4607 
• For reviews on metathesis, see:
• 3a Chang S. Grubbs RH. Tetrahedron  1998,  54:  4413 
• 3b Fürstner A. Angew. Chem. Int. Ed.  2000,  39:  3012 
• 4a Koide K. Finkelstein ZB. Verdine GL. J. Am. Chem. Soc.  2001,  123:  398 
• 4b Miyabe H. Yoshida K. Matsumura A. Yamauchi M. Takemoto Y. Synlett  2003,  567 
• 5a Hu J. Miller MJ. Tetrahedron Lett.  1995,  36:  6379 
• 5b Oyama H, Morita T, and Ono T. inventors; Jap. Pat. Appl., JP  02229175.  ; Chem. Abstr. 1991, 114, 81858
• 5c Carruthers W. Johnstone RAW. J. Chem. Soc.  1965,  1653 
• 7a Wolfe S, and Shustov GPCT. inventors; Int. Appl., WO  0311298.  ; Chem. Abstr. 2003, 138, 153829
• 7b Zong K. Shin SI. Kim HK. Kim HR. Jeon DJ. Ryu EK. Bull. Kor. Chem. Soc.  1999,  20:  965 

6

The Scifinder searches for 1,2-oxazonine, 1,2-oxazecine, and 3-oxo-6,7-dihydro-3H-[1,2]oxazepine hit no known related compounds.

8

Spectral data for 8h: colorless oil; R _f = 0.5 (hexane/EtOAc = 2:1); ¹H NMR (250 MHz, CDCl₃): δ = 5.64-5.53 (m, 2 H), 4.10-4.02 (t, J = 5.6 Hz, 2 H), 3.44-3.35 (t, J = 6.0 Hz, 2 H), 2.48-2.32 (m, 2 H), 2.36-2.24 (m, 2 H), 1.79-1.68 (m, 2 H), 1.49 (s, 9 H); ¹³C NMR (62.9 MHz, CDCl₃): δ = 158.3, 130.8, 128.3, 81.2, 72.6, 52.7, 28.6, 26.2, 25.9, 23.0; IR (film, cm^-1) 2971, 2931, 1729, 1709, 1459, 1393, 1368, 1337, 1164, 1123, 1082; MS: m/z (rel. intensity): 18 (7), 29 (10), 41 (20), 57 (100), 69 (7), 83 (8), 96 (15), 110 (3), 127 (10), 207 (M ⁺ , 1).