A Modified Synthetic Approach to Optically Pure Benzoxazepines from Amino Acid Precursors Using Intramolecular Buchwald-Hartwig C-O Bond-Formation Reaction

Abstract

Palladium-catalyzed intramolecular aryl etherification reaction using bulky binaphthylphosphane ligand is shown to be a convenient method for the synthesis of seven-membered heterocycles. Application of this methodology to a naturally occurring proteinogenic l-amino acid has led to the synthesis of optically active benzoxazepine ring systems of versatile biological importance.

Key words

amino acids - palladium - ligand - etherification - chiral benzoxazepines

References

• 1a Sassa T. Niwa G. Unno H. Ikeda M. Miura Y. Tetrahedron Lett.  1974,  3941 
• 1b Suzuki K. Nozawa K. Udagawa S.-I. Kawai S. Nakajima K.-I. Phytochemistry  1991,  30:  2096 
• 1c Horton DA. Bourne GT. Smythe ML. Chem. Rev.  2003,  103:  893 
• 1d Welmaker GS. Sabalski JE. Tetrahedron Lett.  2004,  45:  4851 
• 1e Costantino L. Barlocco D. Curr. Med. Chem.  2006,  13:  65 
• 1f Lee S.-C. Park SB. Chem. Commun.  2007,  3714 
• 2a Evans BE. Rittle KE. Bock MG. DiPardo RM. Freidinger RM. Whitter WL. Lundell GF. Veber DF. Anderson PS. Chang RSL. Lotti VJ. Carino DJ. Chen TB. Kling PJ. Kunkel KA. Springes JP. Hirshfield J. J. Med. Chem.  1988,  31:  2235 
• 2b Nicolaou KC. Pfefferkorn JA. Roecker AJ. Cao G.-Q. Barluenga S. Mitchell HJ. J. Am. Chem. Soc.  2000,  122:  9939 
• 2c Barluenga J. Valdes C. Chem. Commun.  2005,  4891 
• 3 Kudzma LV. Evans SM. Turnbull SP. Severnak SA. Ezell EF. Bioorg. Med. Chem. Lett.  1995,  5:  1177 
• 4 Toscano L. Grisanti G. Fioriello G. Seghetti E. Bianchetti A. Bossoni G. Riva M. J. Med. Chem.  1976,  19:  208 
• 5a Press JB. Hofmann CM. Eudy NH. Day IP. Greenblatt EN. Safir SR. J. Med. Chem.  1981,  24:  154 
• 5b Liegeois JFF. Rogister FA. Bruhwyler J. Damas J. Nguyen TP. Inarejos MO. Chleide EMG. Mercier MGA. Delarge JE. J. Med. Chem.  1994,  37:  519 
• 5c Kohra T. Tanaka H. Kimura K. Horiuchi H. Seio K. Arita M. Fujimoto T. Yamamoto I. J. Heterocycl. Chem.  2002,  39:  163 
• 6a Standridge RT. inventors; US Patent 4125  538.  ; Chem. Abstr. 1979, 90, 72246r
• 6b Grunewald GL. Dahanukar VH. Ching P. Criscione KR. J. Med. Chem.  1996,  39:  3539 
• 7a Díaz-Gavilán M. Rodríguez-Serrano F. Gómez-Vidal JA. Marchal JA. Aránega A. Gallo MA. Espinosa A. Campos JM. Tetrahedron  2004,  60:  11547 
• 7b Samanta K. Chakravarti B. Mishra JK. Dhar Dwivedi SK. Nayak LV. Choudhry P. Bid HK. Konwar R. Chattopadhyay N. Panda G. Bioorg. Med. Chem. Lett.  2010,  20:  283 
• 8 Swett LR. Stein RG. Kimura ET. J. Med. Chem.  1972,  15:  42 
• 9 Mishra JK. Samanta K. Jain M. Dikshit M. Panda G. Bioorg. Med. Chem. Lett.  2010,  20:  244 
• 10 Miki T. Kori M. Mabuchi H. Banno H. Tozawa R.-I. Nakamura M. Itokawa S. Sugiyama Y. Yukimasa H. Bioorg. Med. Chem.  2002,  10:  401 
• 11a Effland RC. Davis L. J. Heterocycl. Chem.  1985,  22:  1071 
• 11b Ouyang X. Tamayo N. Kiselyov AS. Tetrahedron  1999,  55:  2827 
• 11c Katritzky AR. Xu Y.-J. He H.-Y. J. Chem. Soc., Perkin Trans. 1  2002,  592 
• 11d Margolis BJ. Swidorski JJ. Rogers BN. J. Org. Chem.  2003,  68:  644 
• 11e Omar-Amrani R. Schneider R. Fort Y. Synthesis  2004,  2527 
• 11f Lu S.-M. Alper H.
  J. Am. Chem. Soc.  2005,  127:  14776 
• 11g Ma C. Liu S.-J. Xin L. Falck JR. Shin D.-S. Tetrahedron  2006,  62:  9002 
• 11h Yar M. McGarrigle EM. Aggarwal VK. Org. Lett.  2009,  11:  257 
• 12 Mishra JK. Panda G. J. Comb. Chem.  2007,  9:  321 
• 13 Imramovsky A. Vinšová J. Férriz JM. Kuneš J. Pour M. Dole˛al M. Tetrahedron Lett.  2006,  47:  5007 
• 14a Majhi TP. Achari B. Chattopadhyay P. Heterocycles  2007,  71:  1011 ; and references cited therein
• 14b Neogi A. Majhi TP. Mukhopadhyay R. Chattopadhyay P. J. Org. Chem.  2006,  71:  3291 
• 14c Adhikary ND. Chattopadhyay P. Eur. J. Org. Chem.  2010,  1754 
• 15 Neogi A. Majhi TP. Achari B. Chattopadhyay P. Eur. J. Org. Chem.  2008,  330 
• 16 Bensdira AS. Felix CP. Beatrice M. Guidicelli A. Pascal F. Ferrand S. Perrin M. Lamartini RJ. J. Org. Chem.  2003,  68:  6632 
• 17 Peng W. Forkin H. Valery V. Adv. Synth. Cat.  2006,  348:  1079 
• 18 Nandi A. Mukhopadhyay R. Chattopadhyay P. J. Chem. Soc., Perkin Trans. 1  2001,  3346 
• 19 Giannis A. Sandhoff K. Angew. Chem., Int. Ed. Engl.  1989,  28:  218 
• 20a Bergmeier SC. Seth PP. Tetrahedron Lett.  1999,  40:  6181 
• 20b Moussa Z. Romo D. Synlett  2006,  3294 
• 22a Sheldrick GM. SHELXS-97, Program for Solution of Crystal Structures   University of Göttingen; Germany: 1997. 
• 22b Sheldrick GM. Acta Crystallogr., Ser. A  1990,  46:  467 
• 23 Sheldrick GM. SHELXL-97, Program for Refinement of Crystal Structures   University of Göttingen; Germany: 1997. 
• 24 Kuwabe S.-I. Torraca KE. Buchwald SL. J. Am. Chem. Soc.  2001,  123:  12202 

21

Crystal data of compound 8g: C₂₀H₂₅NO₄S, FW = 375.47, triclinic, space group P1, a = 6.687(4) Å, b = 7.508(5) Å, c = 10.114(6) Å, α = 75.93(4)˚, β = 88.29(4)˚, γ = 80.28(4)˚, V = 485.4(5) Å^³, Z = 1, T = 296(2) K, d _calcd = 1.284 g cm^-³, F(000) = 200. Diffraction data were measured with Mo-Kα (λ = 0.71073 Å) radiation at 296 K using a Bruker Kappa Apex 2 CCD system. A total of 2595 unique reflections were measured (θ_max = 28.18˚). Data analyses were carried out with the Fast Fourier Transform program. The structures were solved by direct methods using the SHELXS-97^²² program. Refinements were carried out with a full matrix least squares method against F2 using SHELXL-97.^²³ Non-hydrogen atoms were refined with anisotropic thermal parameters. The final R value was R1 = 0.0479 and wR2 = 0.1255 with I > 2σ(I). Crystallographic data have been deposited at the Cambridge Crystallographic Data Centre with reference numbers CCDC 776221. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: [phone], E-mail: [e-mail]].