Dipolar Cycloaddition of Dicyclopentadiene with 3-Oxidopyrylium Betaine: An Entry into Methano-Bridged 5-6-7-Fused Ring System

Abstract

The [3+2] cycloaddition of 3-oxidopyrylium ylide, generated from an acetoxypyranone, proceeds with complete chemo- and stereoselectivity. The approach of the dipole takes place exclusively from the exo-face of the bicycloheptane moiety providing a mixture of regioisomers in approximately 55:45 ratio. The derived cycloadduct is then transformed to a novel syn-anti-cis-condensed methano-bridged molecular entity.

Key words

dicyclopentadiene - stereoselective - 3-oxidopyrylium betaine - chemoselective

References

• 1 Pullaiah KC. Surapaneni RK. Rao CB. Albizati KF. Sullivan BW. Faulkner DJ. He CH. Clardy J. J. Org. Chem.  1985,  50:  3665 
• 2 Vasas A. Hohmann J. Forgob P. Szabóc P. Tetrahedron  2004,  60:  5025 
• 3 Peng J. Walsh K. Weedman V. Bergthold JD. Lynch J. Lieu KL. Braude IA. Kelly M. Hamann TK. Tetrahedron  2002,  58:  7809 
• For cycloaddition of 3-oxidopyrylium ylide and its application in the synthesis of natural product see:
• 4a Sammes PG. Street LJ. J. Chem. Soc., Chem. Commun.  1983,  666 
• 4b Wender PA. Rice KD. Schnute ME. J. Am. Chem. Soc.  1997,  119:  7897 
• 4c Wender PA. Jesudason CD. Nakahira H. Tamura N. Tebbe AL. Ueno Y. J. Am. Chem. Soc.  1997,  119:  12976 
• 4d Bauta W. Booth J. Bos ME. DeLuca M. Diorazio L. Donohoe T. Magnus N. Magnus P. Mendoza J. Pye P. Tarrant J. Thom S. Ujjainwalla F. Tetrahedron Lett.  1995,  36:  5327 
• 4e Ohmori N. J. Chem. Soc., Perkin Trans. 1  2002,  755 
• 4f Marshall KA. Mapp AK. Heathcock CH. J. Org. Chem.  1996,  61:  9135 
• 4g Baldwin JE. Mayweg AVW. Pritchard GJ. Adlington RM. Tetrahedron Lett.  2003,  44:  4543 
• 4h Celanire S. Marlin F. Baldwin JE. Adlington RM. Tetrahedron  2005,  61:  3025 
• 4i Tang B. Bray CD. Pattenden G. Tetrahedron Lett.  2006,  47:  6401 
• 4j Snider BB. Grabowski JF. Tetrahedron  2006,  62:  5171 
• 4k Snider BB. Wu X. Nakamura S. Hashimoto S. Org. Lett.  2007,  9:  873 
• 4l Singh VK. Muralikrishna U. . Trivedi GK. Tetrahedron  2008,  64:  3405 ; and pertinent references cited therein
• 5 Hendrickson JB. Farina JS. J. Org. Chem.  1980,  45:  3359 
• 6a Sammes PG. Street LJ. J. Chem. Soc., Perkin Trans. 1  1983,  1261 
• 6b Sammes PG. Gazz. Chim. Ital.  1986,  51:  1573 
• 6c Sammes PG. Street LJ. J. Chem. Soc., Chem. Commun.  1982,  1056 
• 6d Sammes PG. Street LJ. J. Chem. Soc., Perkin Trans. 1  1983,  2729 
• 6e Sammes PG. Street LJ. J. Chem. Soc., Chem. Commun.  1983,  666 
• 6f Sammes PG. Whitby RJ. J. Chem. Soc., Chem. Commun.  1984,  702 
• 6g Sammes PG. Whitby RJ. J. Chem. Soc., Chem. Commun.  1986,  281 
• 6h Archer DA. Bromidge S. Sammes PG. J. Chem. Soc., Perkin Trans. 1  1988,  3223 
• 7a Bast K. Christl M. Huisgen R. Mack W. Chem. Ber.  1973,  106:  3312 
• 7b Namboothiri INN. Rastogi N. Ganguly B. Shaikh MM. Miriam C. Tetrahedron  2004,  60:  1453 
• 8 Georgiadis MP. Couladouros EA. J. Org. Chem.  1986,  51:  2725 
• 10 Khurana JM. Sharma P. Bull. Chem. Soc. Jpn.  2004,  77:  549 ; and references cited therein
• 11 Bromidge SM. Sammes PG. Street LJ. J. Chem. Soc., Perkin Trans. 1  1985,  1725 
• 12 Wharton PS. Bohlen DH. J. Org. Chem.  1961,  26:  3615 

9

Selected X-ray crystallographic data for 7 (C₁₅H₁₆O₂): space group: orthorhombic, Pbna; unit cell dimensions: a = 7.7630 (18) Å, b = 12.0930 (5) Å, c = 24.0210 (14) Å; V = 55.0(5) ų; Z = 8, D _calc = 1.345 Mg/m^-3; absorption coefficient = 0.088 mm^-1. Complete crystallographic data (excluding structure factors) for this structure have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication number CCDC 679327. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: [phone] or e-mail: [e-mail]].

13

Selected X-ray crystallographic data for 14a (C₁₇H₂₀O₃): unit cell contains two molecules, for simplicity only one molecule is shown in Figure [3] ; space group: monoclinic P21/c; unit cell dimensions: a = 10.2468 (16) Å, b = 8.7716 (12) Å, c = 31.016 (8) Å; V = 2748.1 (9) ų; Z = 4, D _calc = 1.316 Mg/m^-3; absorption coefficient = 0.089 mm^-1. Complete crystallographic data (excluding structure factors) for this structure have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication number CCDC 679328. Copies of the data can be obtained, free of charge, on application to CCDC.