Reactions of o-Aminothiophenol and o -Aminophenyl Disulfide with Itaconic Anhydride and (-)-Dimenthyl Itaconate: Access to Enantiomerically Pure 1,5-Benzothiazepines and Benzothiazolyl-2-methylacrylic Acid [1]

Abstract

A facile chemo- and regioselective reactions of o-aminothiophenol (o-ATP) with itaconic anhydride is described. 1,5-Benzothiazepinyl-3-acetic acid is obtained in 81% yield via the exclusive Michael type addition of the thiol unit from o-ATP to the carbon-carbon double bond in itaconic anhydride followed by an intramolecular anhydride ring opening with an amine unit. The moderately stereoselective Michael type addition of the thiol unit from o-ATP to (-)-dimenthyl itaconate to obtain a mixture of dia­stereomers in a 7:3 ratio in 82% yield has been demonstrated. The reductive sulfur-sulfur bond cleavage in the dicarboxylic acid, 2-({2-[2-(3-carboxybut-3-enoylamino)phenyldisulfanyl]phenylcarbamoyl}methyl)acrylic acid, to the corresponding benzothiazolyl-2-methylacrylic acid in 84% yield, instead of the desired benzothioazocine is also reported.

Key words

o-aminothiophenol - itaconic anhydride - dimenthyl itaconate - chemo- - regio- and stereoselective reactions - benzothiazepines - benzothiazoles - synthesis

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NCL Communication No. 6697.

References

• 2a Abe K. Inoue H. Nagao T. Yakugaku Zasshi  1988,  108:  716 ; Chem. Abstr. 1989, 111, 39202c
• 2b The Merck Index   13th ed.:  Merck & Co.; Rahway N. J.: 2001. 
• 2c Comprehensive Natural Products Chemistry   Vol. 1-8:  Barton DS. Nakanishi K. Meth-Cohn O. Pergamon; London: 1999. 
• 2d Advances in Heterocyclic Chemistry   Vol. 1-86:  Katritzky AR. Academic Press; New York: 1962-2004. 
• 2e Advances in Drug Research   Vol. 1-30:  Testa B. Mayer UA. Academic Press; New York: 1966-1996. 
• 2f Baker DR. Fenyes JG. Moberg WK. Cross B. Synthesis and Chemistry of Agrochemicals   ACS Symposium Series 355, American Chemical Society; Washington: 1987. 
• 3a Visch H.-J. Rutter GA. Koopman WJH. Koenderink JB. Verkaart S. de Groot T. Varadi A. Mitchell KJ. van der Heuvel LP. Smeitink JAM. Willems PHGM. J. Biol. Chem.  2004,  279:  40328 
• 3b Slade J. Stanton JL. Ben-David D. Mazzenga GC. J. Med. Chem.  1985,  28:  1517 
• 3c Santos LC. Mourao RHV. Uchoa FT. Silva TG. Malta DJN. Moura RO. Lima MCA. Galdino SL. Pitta IR. Barbe J. Heterocycl. Commun.  2005,  11:  433 
• 3d McGee MM. Gemma S. Butini S. Ramunno A. Zisterer DM. Fattorusso C. Catalanotti B. Kukreja G. Fiorini I. Pisano C. Cucco C. Novellino E. Nacci V. Williams DC. Campiani G. J. Med. Chem.  2005,  48:  4367 
• 3e Inoue H. Konda M. Hashiyama T. Ostuka H. Takahashi K. Gaino M. Date T. Aoe K. Takeda M. Murata S. Narita H. Nagao T. J. Med. Chem.  1991,  34:  675 
• 3f Atwal KS. Bergey JL. Hedberg A. Moreland S. J. Med. Chem.  1987,  30:  635 
• 3g Inoue H. Konda M. Hashiyama T. Otsuka H. Watanabe A. Gaino M. Takahashi K. Date T. Okamura K. Takeda M. Narita H. Murata S. Odawara A. Sasaki H. Nagao T. Chem. Pharm. Bull.  1997,  45:  1008 
• 3h Micheli F. Degiorgis F. Feriani A. Paio A. Pozzan A. Zarantonello P. Seneci P. J. Comb. Chem.  2001,  3:  224 
• 3i Avram S. Milac A.-L. Flonta ML. Curr. Computer-Aided Drug Design  2005,  1:  347 
• 3j Pei Y. Lilly MJ. Owen DJ. D’Souza LJ. Tang X.-Q. Yu J. Nazarbaghi R. Hunter A. Anderson CM. Glasco S. Ede NJ. James IW. Maitra U. Chandersekaran S. Moos WH. Ghosh SS. J. Org. Chem.  2003,  68:  92 
• 3k Kohno M. Yano M. Kobayashi S. Doi M. Oda T. Tokuhisa T. Okuda S. Ohkusa T. Kohno M. Matsuzaki M. Am. J. Physiol.  2003,  284:  H1035 
• 3l Ambrogi V. Grandolini G. Perioli L. Ricci M. Rossi C. Tuttobello L. Eur. J. Med. Chem.  1990,  25:  403 
• 3m Grandolini G. Perioli L. Ambrogi V. Eur. J. Med. Chem.  1999,  34:  701 
• 4a Prakash O. Kumar A. Sadana A. Prakash R. Singh SP. Claramunt RM. Sanz D. Alkorta I. Elguero J. Tetrahedron  2005,  61:  6642 
• 4b Amblard M. Raynal N. Averlant PM.-C. Didierjean C. Calmes M. Fabre O. Aubry A. Marraud M. Martinez J. Tetrahedron Lett.  2005,  46:  3733 
• 4c Van Otterlo WAL. Morgans GL. Khanye SD. Aderibigbe BAA. Michael JP. Billing DG. Tetrahedron Lett.  2004,  45:  9171 
• 4d Giordano C. Restelli A. Tetrahedron: Asymmetry  1991,  2:  785 
• 4e Yang X. Buzon L. Hamanaka E. Liu KK.-C. Tetrahedron: Asymmetry  2000,  11:  4447 
• 5a Balasubramaniyan V. Balasubramaniyan P. Shaikh AS. Argade NP. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.  1989,  28:  123 
• 5b Okafor CO. Akpuaka MU. J. Chem. Soc., Perkin Trans. 1  1993,  159 
• 5c Balasubramaniyan V. Balasubramaniyan P. Shaikh AS. Tetrahedron  1986,  42:  2731 
• 5d Deshpande AM. Natu AA. Argade NP. Heterocycles  1999,  51:  2159 
• 5e Teitei T. Aust. J. Chem.  1986,  39:  503 
• 5f Kaul BL. Helv. Chim. Acta  1974,  57:  2664 
• 6a Desai SB. Argade NP. J. Org. Chem.  1997,  62:  4862 
• 6b Deshpande AM. Natu AA. Argade NP. J. Org. Chem.  1998,  63:  9557 
• 6c Mhaske SB. Argade NP. J. Org. Chem.  2001,  66:  9038 
• 6d Kar A. Argade NP. J. Org. Chem.  2002,  67:  7131 
• 6e Kar A. Argade NP. Tetrahedron  2003,  59:  2991 
• 6f Gogoi S. Argade NP. Tetrahedron  2004,  60:  9093 
• 6g Haval KP. Mhaske SB. Argade NP. Tetrahedron  2006,  62:  937 
• 6h Gogoi S. Argade NP. Tetrahedron  2006,  62:  2715 
• 6i Gogoi S. Argade NP. Tetrahedron  2006,  62:  2999 
• 6j Haval KP. Argade NP. Tetrahedron  2006,  62:  3557 
• 6k Easwar S. Argade NP. Synthesis  2006,  831 ; and references cited therein
• 7a Miyata O. Shinada T. Ninomiya I. Naito T. Tetrahedron Lett.  1991,  32:  3519 
• 7b Miyata O. Shinada T. Naito T. Ninomiya I. Date T. Okamura K. Tetrahedron  1993,  49:  8119 ; and references cited therein
• 8a Argade NP. Balasubramaniyan V. Heterocycles  2000,  53:  475 
• 8b Gholap AD. Patel MV. Patil RC. Balasubramaniyan P. Balasubramaniyan V. Indian J. Chem. Educ.  1980,  7:  26 ; and references cited therein
• 9 Eliel EL. Stereochemistry of Carbon Compounds   TMH Edition; New Delhi: 1975.  Chap. 7. p.180 

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NCL Communication No. 6697.

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Crystallographic data (excluding structure factors) for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication numbers CCDC 600537 and 600538. 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]].