Regioselective Synthesis of Oxepin- and Oxocin-Annulated Quinolines by Combined ‘Claisen-Rearrangement/Olefin-Metathesis’ Reactions

Abstract

Oxepin- and oxocin-fused quinolines were prepared by a combined Claisen-rearrangement/ring-closing metathesis approach. The metathesis reactions proceeded in good yields despite the presence of the lone pair of the nitrogen atom of the quinoline moiety. The formation of a hydrochloride salt was not necessary.

Key Words

cyclization - heterocycles - rearrangement - ring-closing metathesis

References

• Reviews:
• 1a Schuster M. Blechert S. Angew. Chem., Int. Ed. Engl.  1997,  36:  2036 
• 1b Armstrong SK. J. Chem. Soc., Perkin Trans. 1  1998,  371 
• 1c Grubbs RH. Chang S. Tetrahedron  1998,  54:  4413 
• 1d Trnka TM. Grubbs RH. Acc. Chem. Res.  2001,  34:  18 
• 1e Fürstner A. Angew. Chem. Int. Ed.  2000,  39:  3012 
• 1f Blechert S. Connon S. Angew. Chem. Int. Ed.  2003,  42:  1900 
• 1g Poulson CS. Madsen R. Synthesis  2003,  1 
• For recent reviews on Claisen rearrangements, see:
• 2a Nubbemeyer U. Synthesis  2003,  961 
• 2b Castro AMM. Chem. Rev.  2004,  104:  2939 
• 2c Blechert S. Synthesis  1989,  71 
• 3a Kotha S. Mandal K. Tiwari A. Mobin SM. Chem. Eur. J.  2006,  12:  8024 
• 3b Kotha S. Mandal K. Tetrahedron Lett.  2004,  45:  1391 
• 4 Chattopadhyay SK. Dey R. Biswas S. Synthesis  2005,  403 
• 5 Majumdar KC. Rahaman H. Islam R. Roy B. Tetrahedron Lett.  2006,  47:  2111 
• 6 Pain C. Célanire S. Guillaumet G. Joseph B. Synlett  2003,  2089 
• 7 For the biological activity of 1,2,3,3a,4,9b-hexahydro-5-oxa-1,8-diazacyclopenta[a]naphthalene, see: Vernier J.-M. Holsenback H. Cosford NDP. Whitten JP. Menzaghi F. Bioorg. Med. Chem. Lett.  1998,  8:  2173 
• 8 For furoerioaustralasine, see: da Cunha EVL. Armstrong JA. Gray AI. Hockless DCR. Waterman PG. White AH. Aust. J. Chem.  1993,  46:  1507 
• 9a Wang Y.-G. Lin X.-F. Cui S.-L. Synlett  2004,  1175 
• 9b Li H. Yang H. Petersen JL. Wang KK. J. Org. Chem.  2004,  69:  4500 
• 10 Kurita J. Kakusawa N. Yasuike S. Tsuchiya T. Heterocycles  1990,  31:  1937 
• 11a Sabui SK. Venkateswaran RV. Tetrahedron Lett.  2004,  45:  983 
• 11b Kishuku H. Scindo M. Shishido K. Chem. Commun.  2003,  350 
• 11c Stefinovic M. Snieckus V. J. Org. Chem.  1998,  63:  2808 
• 11d Macias FA. Varela RM. Torres A. Molinillo JMG. Tetrahedron Lett.  1999,  40:  4725 
• 11e Macias FA. Molinillo JMG. Varala RM. Torres A. Fronzek FR. J. Org. Chem.  1994,  59:  8261 
• 12a Cassis R. Tapia R. Valderrama JA. Synth. Commun.  1985,  15:  125 
• For N-allylation of quinolines, see:
• 12b Koga H. Itoh A. Murayama S. Suzue S. Irikura T. J. Med. Chem.  1980,  23:  1358 
• 13 Salzer W. Timmler H. Andersag H. Chem. Ber.  1948,  81:  12 
• For related problems on pyridine-metal coordination, see:
• 14a Ling Ng P. Lambert JN. Synlett  1999,  1749 
• 14b Raatz D. Innertsberger C. Reiser O. Synlett  1999,  1907 
• 15 Felpin F.-X. Girard S. Vo-Thanh G. Robins RJ. Villiéras J. Lebreton J. J. Org. Chem.  2001,  66:  6305 
• 16a Fu GC. Nguyen SBT. Grubbs RB. J. Am. Chem. Soc.  1993,  115:  9856 
• 16b Evans P. Grigg R. York M. Tetrahedron Lett.  2000,  41:  3967 
• 17 Grigg R. Sridharan V. York M. Tetrahedron Lett.  1998,  39:  4139 

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