Download PDF
Synthesis 2011(8): 1261-1266  
DOI: 10.1055/s-0030-1258476
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

N-Thioaroylmorpholines in Silica Gel-Water: An Efficient System to Access Functionalized Allylic Thioesters from Baylis-Hillman Bromides

Rajesh Patel, Vishnu P. Srivastava, Lal Dhar S. Yadav*
Green Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad 211 002, India
Fax: +91(532)2460533; e-Mail: ldsyadav@hotmail.com;
Further Information

Publication History

Received 29 December 2010
Publication Date:
14 March 2011 (online)

   Permissions and Reprints All articles of this category
Preview

Abstract

A facile, one-pot synthesis of allylic thioesters starting from Baylis-Hillman (BH) bromides and N-thioaroylmorpholines is described. The synthesis is performed in a silica gel-water system without any additional catalyst or co-catalyst. The reaction pathway involves selective S-alkylation of N-thioaroylmorpholines via nucleophilic displacement (SN2) with BH bromides, followed by hydrolysis to afford the corresponding thioesters. The present synthetic protocol avoids the application of malodorous sulfur compounds of limited accessibility such as thiols, and thioacids and their salts as reactants.

Key words

Baylis-Hillman adducts - aqueous medium - allylic thioesters - nucleophilic displacement - green chemistry - regioselectivity

    References

  • 1a Wu H. Lin W. Wan Y. Xin H.-Q. Shi D.-Q. Shi Y.-H. Yuan R. Bo R.-C. Yin W. J. Comb. Chem.  2010,  12:  31 
    Search in Google Scholar
  • 1b Basu B. Paul S. Nanda AK. Green Chem.  2009,  11:  1115 
    Search in Google Scholar
  • 1c Spagnol G. Rajca A. Rajca S. J. Org. Chem.  2007,  72:  1867 
    Search in Google Scholar
  • 2a Minakata S. Kano D. Oderaotoshi Y. Komatsu M. Angew. Chem. Int. Ed.  2004,  43:  79 
    Search in Google Scholar
  • 2b Minakata S. Komatsu M. Chem. Rev.  2009,  109:  711 
    Search in Google Scholar
  • 3 Kondo T. Mitsudo T.-A. Chem. Rev.  2000,  100:  3205 
    CrossrefPubMedSearch in Google Scholar
  • 4a Norcross RD. Paterson I. Chem. Rev.  1995,  95:  2041 
    Search in Google Scholar
  • 4b Faulkner DJ. Nat. Prod. Rep.  1995,  12:  223 
    Search in Google Scholar
  • 4c Liu G. Link JT. Pei Z. Reilly EB. Leitza S. Nguyen B. Marsh KC. Okasinski GF. von Geldern TW. Ormes M. Fowler K. Gallatin M. J. Med. Chem.  2000,  43:  4025 
    Search in Google Scholar
  • 4d Sawyer JS. Schmittling EA. Palkowitz JA. Smith WJ. J. Org. Chem.  1998,  63:  6338 
    Search in Google Scholar
  • 4e Kita Y. Iio K. Kawaguchi K.-I. Fukuda N. Takeda Y. Ueno H. Okunaka R. Higuchi K. Tsujino T. Fujioka H. Akai S. Chem. Eur. J.  2000,  6:  3897 
    Search in Google Scholar
  • 5a Kanda Y. Ashizawa T. Kakita S. Takahashi Y. Kono M. Yoshida M. Saitoh Y. Okabe M. J. Med. Chem.  1999,  42:  1330 
    Search in Google Scholar
  • 5b Mroszczak E, and Runkel R. inventors; U.S. Patent  4397862.  ; Chem. Abstr. 1983, 99, 146134
  • 5c Venuti MC. Young GM. Maloney PG. Johnson D. McGreevy K. Pharm. Res.  1989,  6:  867 
    Search in Google Scholar
  • 5d Greenlee ML. Laub JB. Balkovec JM. Hammond ML. Hammond GG. Pompliano DL. Epstein-Toney JH. Bioorg. Med. Chem. Lett.  1999,  9:  2549 
    Search in Google Scholar
  • 5e Olsen J. Bjørnsdottir I. Tjørnelund J. Hansen SH. J. Pharm. Biomed. Anal.  2002,  29:  7 
    Search in Google Scholar
  • 5f Stachelhaus T. Huser A. Marahiel MA. Chem. Biol.  1996,  3:  913 
    Search in Google Scholar
  • 5g Dittmann J. Wenger RM. Kleinkauf H. Lawen A. J. Biol. Chem.  1994,  269:  2841 
    Search in Google Scholar
  • 6a Matsumoto K. Costner EA. Nishimura I. Ueda M. Willson CG. Macromolecules  2008,  41:  5674 
    Search in Google Scholar
  • 6b Kricheldorf HR. Schwarz G. J. Macromol. Sci., Part A: Pure Appl. Chem.  2007,  44:  625 
    Search in Google Scholar
  • 6c Kameyama A. Kimura Y. Nishikubo T. Macromolecules  1997,  30:  6494 
    Search in Google Scholar
  • 7a Fujiwara S.-I. Kambe N. Top. Curr. Chem.  2005,  251:  87 
    Search in Google Scholar
  • 7b Yang W. Drueckhammer DG. J. Am. Chem. Soc.  2001,  123:  11004 
    Search in Google Scholar
  • 7c Wiberg KB. J. Chem. Educ.  1996,  73:  1089 
    Search in Google Scholar
  • 7d Cronyn MW. Chang MP. Wall RA.
    J. Am. Chem. Soc.  1955,  77:  3031 
    Search in Google Scholar
  • 8a Yang W. Drueckhammer DG. J. Am. Chem. Soc.  2001,  123:  11004 
    Search in Google Scholar
  • 8b Wiberg KB. J. Chem. Educ.  1996,  73:  1089 
    Search in Google Scholar
  • 8c Cronyn MW. Chang MP. Wall RA. J. Am. Chem. Soc.  1955,  77:  3031 
    Search in Google Scholar
  • 8d Johnson JS. Evans DA. Acc. Chem. Res.  2000,  33:  325 
    Search in Google Scholar
  • 8e Fortner KC. Shair MD. J. Am. Chem. Soc.  2007,  129:  1032 
    Search in Google Scholar
  • 8f Gennari C. Vulpetti A. Pain G. Tetrahedron  1997,  53:  5909 
    Search in Google Scholar
  • 9a Villalobos JM. Srogl J. Liebeskind LS. J. Am. Chem. Soc.  2007,  129:  15734 
    Search in Google Scholar
  • 9b Prokopcova H. Pisani L. Kappe CO. Synlett  2007,  43 
  • 9c Lengar A. Kappe CO. Org. Lett.  2004,  6:  771 
    Search in Google Scholar
  • 9d Fukuyama T. Lin S.-C. Li L. J. Am. Chem. Soc.  1990,  112:  7050 
    Search in Google Scholar
  • 9e Ficht S. Payne RJ. G uy RT. Wong CH. Eur. J. Org. Chem.  2008,  3620 
  • 9f Ozawa C. Katayama H. Hojo H. Yuko N. Yoshiaki N. Org. Lett.  2008,  10:  3531 
    Search in Google Scholar
  • 9g McGarvey GJ. Williams JM. Hiner RN. Matsubara Y. Oh T. J. Am. Chem. Soc.  1986,  108:  4943 
    Search in Google Scholar
  • 10a Halcomb R. J. Am. Chem. Soc.  1995,  117:  5720 
    Search in Google Scholar
  • 10b Corey EJ. Reichard G. J. Am. Chem. Soc.  1992,  114:  10677 
    Search in Google Scholar
  • 10c Ashizawa T. Kawashima K. Kanda Y. Gomi K. Okabe M. Ueda K. Tamaoki T. Anti-Cancer Drugs  1999,  10:  829 
    Search in Google Scholar
  • 10d Murai T. Kakami K. Hayashi A. Komuro T. Takada H. Fujii M. Karida T. Kato S.
    J. Am. Chem. Soc.  1997,  119:  8592 
    Search in Google Scholar
  • 10e Vogel KW. Drueckhanmer DG. J. Am. Chem. Soc.  1998,  120:  3275 
    Search in Google Scholar
  • 10f Wallace OB. Springer DM. Tetrahedron Lett.  1998,  39:  2693 
    Search in Google Scholar
  • 11a Harding RL. Bugg TDH. Tetrahedron Lett.  2000,  41:  2729 
    Search in Google Scholar
  • 11b Iwama T. Kataoka T. Muraoka O. Tanabe G. J. Org. Chem.  1998,  63:  8355 
    Search in Google Scholar
  • 11c Brown RS. Aman A. J. Org. Chem.  1997,  62:  4816 
    Search in Google Scholar
  • 11d Um P.-J. Drueckhammer DG. J. Am. Chem. Soc.  1998,  120:  5605 
    Search in Google Scholar
  • 11e Buchi G. Pawlak M. J. Org. Chem.  1975,  40:  100 
    Search in Google Scholar
  • 11f Schmittberger T. Cotte A. Waldmann H. J. Chem. Soc., Chem. Commun.  1998,  937 
  • 12a Page PCB. Wilkes RD. Reynolds D. In Comprehensive Organic Functional Group Transformations   Vol. 2:  Katritzky AR. Meth-Cohn O. Rees CW. Ley SV. Pergamon; Oxford: 1995.  p.113 
    Search in Google Scholar
  • 12b Mann G. Baranano D. Hartwig JF. Rheingold AL. Guzei IA. J. Am. Chem. Soc.  1998,  120:  9205 
    Search in Google Scholar
  • 12c Zheng N. McWilliams JC. Fleitz FJ. Armstrong JD. Volante RP. J. Org. Chem.  1998,  63:  9606 
    Search in Google Scholar
  • 13a Penn GH. Liu F. J. Org. Chem.  1994,  59:  2608 
    Search in Google Scholar
  • 13b Khan AT. Choudry LH. Ghosh S. Eur. J. Org. Chem.  2005,  2782 
  • 13c Chandra KL. Saravan P. Singh RK. Singh VK. Tetrahedron  2002,  58:  1369 
    Search in Google Scholar
  • 13d Spessard G. Chan W. Masamune S. Org. Synth.  1982,  61:  134 
    Search in Google Scholar
  • 13e Yamamoto H, Fukazu N, Tanaka M, and Kobayashi S. inventors; Jpn. Kokai Tokkyo Koho  JP 2004300110.  ; Chem. Abstr. 2004, 141, 349818
  • 13f Li H. Zu L. Wang J. Wang W. Tetrahedron Lett.  2006,  47:  3145 
    Search in Google Scholar
  • 13g Li H. Wang J. Zu L. Wang W. Tetrahedron Lett.  2006,  47:  2585 
    Search in Google Scholar
  • 13h Busque F. March PD. Figueredo M. Font J. Gonzalez L. Eur. J. Org. Chem.  2004,  1492 
  • 13i Aoyama T. Takido T. Kodomari M. Synth. Commun.  2003,  33:  3817 
    Search in Google Scholar
  • 14a Gopinath P. Debasree C. Vidyarini RS. Chandrasekaran S. Tetrahedron  2010,  66:  7001 
    Search in Google Scholar
  • 14b Boeini HZ. Mobin M. Synlett  2010,  2861 
  • 14c Boeini HZ. Kashan ME. Green Chem.  2009,  11:  1987 
    Search in Google Scholar
  • 14d Gopinath P. Vidyarini RS. Chandrasekaran S.
    J. Org. Chem.  2009,  74:  6291 
    Search in Google Scholar
  • 15a Lussem BJ. Gais H.-J. J. Org. Chem.  2004,  69:  4041 
    Search in Google Scholar
  • 15b Pearson AJ. Alimardanov A. Pinkerton AA. Parrish DA. J. Org. Chem.  1998,  63:  6610 
    Search in Google Scholar
  • 15c Mikojczk M. Dabrowwicz J. Kieasinski P. Chiral Sulfur Reagents   CRC Press; Boca Raton: 1997. 
  • 15d Katritzky AR. Piffl M. Lang H. Anders E. Chem. Rev.  1999,  99:  665 
    Search in Google Scholar
  • 15e Reggelin M. Zur C. Synthesis  2000,  1 
  • 16a Baylis AB, and Hillaman MED. inventors; Offenlegungsschrift 2155113, U.S. Patent  3,743,669.  ; Chem. Abstr. 1972, 77, 34174q
  • 16b Organic Reactions   Vol. 51:  Ciganek E. Wiley; New York: 1997.  p.201-305  
  • 16c Morita K. Suzuki Z. Hirose H. Bull. Chem. Soc. Jpn.  1968,  41:  2815 
    Search in Google Scholar
  • 17a Basavaiah D. Reddy BS. Badsara SS. Chem. Rev.  2010,  110:  5447 
    Search in Google Scholar
  • 17b Declerck V. Martinez J. Lamaty F. Chem. Rev.  2009,  109:  1 
    Search in Google Scholar
  • 17c Ma G.-N. Jiang J.-J. Shi M. Wei Y. Chem. Commun.  2009,  5496 
  • 17d Singh V. Batra S. Tetrahedron  2008,  64:  4511 
    Search in Google Scholar
  • 17e Basavaiah D. Rao KV. Reddy RJ. Chem. Soc. Rev.  2007,  36:  1581 
    Search in Google Scholar
  • 17f Basavaiah D. Rao AJ. Satyanarayana T. Chem. Rev.  2003,  103:  811 
    Search in Google Scholar
  • 18 Kabalka GW. Venkataiah B. Dong G. Tetrahedron Lett.  2003,  44:  4673 
    CrossrefSearch in Google Scholar
  • 19a Liu Y. Xu D. Xu Z. Zhang Y. Heteroat. Chem.  2008,  19:  188 
    Search in Google Scholar
  • 19b Das B. Chowdhury N. Damodar K. Banerjee J. Chem. Pharm. Bull.  2007,  55:  1274 
    Search in Google Scholar
  • 19c Kamimura A. Morita R. Matsuura K. Omata Y. Shirai M. Tetrahedron Lett.  2002,  43:  6189 
    Search in Google Scholar
  • 19d Binay P, Henary JC, Vidal V, Genet JP, and Dellis P. inventors; Fr. Demande  FR2772027.  ; Chem. Abstr. 1999, 131, 170171
  • 19e Deane PO. Guthrie-Strachan JJ. Kaye PT. Whittaker RE. Synth. Commun.  1998,  28:  2601 
    Search in Google Scholar
  • 20a Shrihari P. Singh AP. Jain R. Yadav JS. Synthesis  2006,  2772 
  • 20b Sa MM. Fernandes L. Ferreira M. Bortoluzzi AJ. Tetrahedron Lett.  2007,  48:  1228 
    Search in Google Scholar
  • 21 Cha MJ. Song YS. Lee K.-J. Bull. Korean Chem. Soc.  2006,  27:  1900 
    CrossrefSearch in Google Scholar
  • 22a Yadav LDS. Srivastava VP. Patel R. Tetrahedron Lett.  2008,  49:  3142 
    Search in Google Scholar
  • 22b Yadav LDS. Srivastava VP. Patel R. Tetrahedron Lett.  2008,  49:  5652 
    Search in Google Scholar
  • 22c Yadav LDS. Patel R. Srivastava VP. Synlett  2008,  1789 
  • 22d Yadav LDS. Patel R. Srivastava VP. Tetrahedron Lett.  2009,  50:  1335 
    Search in Google Scholar
  • 22e Yadav LDS. Srivastava VP. Patel R. Tetrahedron Lett.  2009,  50:  1423 
    Search in Google Scholar
  • 22f Yadav LDS. Srivastava VP. Patel R. Synlett  2010,  1047 
  • 23 Mason PH. Emslie ND. Tetrahedron  1994,  50:  21001 
    Search in Google Scholar
  • 24 Singh V. Pathak R. Batra S. Catal. Commun.  2007,  8:  2048 
    CrossrefSearch in Google Scholar
  • 25a Zbruyev OI. Stiasni N. Kappe CO. J. Comb. Chem.  2003,  5:  145 
    Search in Google Scholar
  • 25b Buchholz R. Hoffmann HMR. Helv. Chim. Acta  1991,  74:  1213 
    Search in Google Scholar
  • 25c Basavaiah D. Hyma RS. Padmaja K. Krishnamacharyulu M. Tetrahedron  1999,  55:  6971 
    Search in Google Scholar
  • 25d Basavaiah D. Krishnamacharyulu M. Hyma RS. Sarma PKS. Kumaragurubaran N. J. Org. Chem.  1999,  64:  1197 
    Search in Google Scholar