Synthesis 2015; 47(19): 2965-2970
DOI: 10.1055/s-0034-1380451
special topic
© Georg Thieme Verlag Stuttgart · New York

Efficient Synthesis of 3-Alkynyl-2-(hydroxymethyl)cyclohex-2-en-1-ones by a Stork–Danheiser Sequence from Vinylogous Esters and Terminal Alkynes

Amarchand Parida
Department of Chemistry, Indian Institute of Science Education and Research, Bhopal, MP 462066, India   Email: alakesh@iiserb.ac.in
,
Mohd. Sharique
Department of Chemistry, Indian Institute of Science Education and Research, Bhopal, MP 462066, India   Email: alakesh@iiserb.ac.in
,
Badrinath N. Kakde
Department of Chemistry, Indian Institute of Science Education and Research, Bhopal, MP 462066, India   Email: alakesh@iiserb.ac.in
,
Santanu Ghosh
Department of Chemistry, Indian Institute of Science Education and Research, Bhopal, MP 462066, India   Email: alakesh@iiserb.ac.in
,
Alakesh Bisai*
Department of Chemistry, Indian Institute of Science Education and Research, Bhopal, MP 462066, India   Email: alakesh@iiserb.ac.in
› Author Affiliations
Further Information

Publication History

Received: 25 April 2015

Accepted after revision: 24 May 2015

Publication Date:
06 July 2015 (eFirst)

Abstract

An efficient Stork–Danheiser sequence has been developed for the preparation of a variety of 3-alkynyl-2-(hydroxymethyl)cyclohex-2-en-1-ones in good to excellent yields from the corresponding 4,6,7,8-tetrahydro-5H-1,3-benzodioxin-5-ones and terminal alkynes. Several of the 3-alkynyl-2-(hydroxymethyl)cyclohex-2-en-1-one products were catalytically cyclized to give the corresponding 3-aryl-1,5,6,7-tetrahydro-8H-isochromen-8-ones.

Supporting Information

 
  • References

    • 1a Harinantenaina L, Quang DN, Takeshi N, Hashimoto T, Kohchi C, Soma G.-I, Asakawa Y. J. Nat. Prod. 2005; 68: 1779
    • 1b Asakawa Y. Prog. Chem. Org. Nat. Prod. 1995; 65: 1
    • 1c Li R.-J, Zhao Y, Tokuda H, Yang X.-M, Wang Y.-H, Shi Q, Morris-Natschke SL, Lou H.-X, Lee K.-H. Tetrahedron Lett. 2014; 55: 6500
  • 2 Friederich S, Maier UH, Deus-Neumann B, Asakawa Y, Zenk MH. Phytochemistry 1999; 50: 589
    • 3a Ohta Y, Abe S, Komura H, Kobayashi M. J. Am. Chem. Soc. 1983; 105: 4480
    • 3b Valio IF. M, Burdon RS, Schwabe WW. Nature 1969; 223: 1176
  • 4 For a synthetic approach to lunularic acid (1d), see: Nguyen T.-H, Castanet A.-S, Mortier J. Org. Lett. 2006; 8: 765
  • 5 For isolation of 1e,f, see: Bader A, De Tommasi N, Cotugno R, Braca A. J. Nat. Prod. 2011; 74: 1421
    • 6a Sun H, Ho CL, Ding F, Soehano I, Liu X.-W, Liang Z.-X. J. Am. Chem. Soc. 2012; 134: 11924

    • For an excellent review, see:
    • 6b Butler MS. Nat. Prod. Rep. 2008; 25: 475
    • 6c Bianchi DA, Blanco NE, Carrillo N, Kaufman TS. J. Agric. Food Chem. 2004; 52: 1923
    • 6d McInerney BV, Taylor WC, Lacey MJ, Akhurst RJ, Gregson RP. J. Nat. Prod. 1991; 54: 785

      For synthetic approaches to isocoumarin derivatives, see:
    • 7a Kotsuki H, Araki T, Miyazaki A, Iwasaki M, Datta PK. Org. Lett. 1999; 1: 499
    • 7b Patel SK, Murat K, Py S, Vallée Y. Org. Lett. 2003; 5: 4081
    • 7c Enomoto M, Kuwahara S. J. Org. Chem. 2009; 74: 7566
    • 7d Cai S, Wang F, Xi C. J. Org. Chem. 2012; 77: 2331
    • 7e Nandi D, Ghosh D, Chen S.-J, Kuo B.-C, Wang NM, Lee HM. J. Org. Chem. 2013; 78: 3445
    • 8a Matsuda H, Shimoda H, Yamahara J, Yoshikawa M. Biol. Pharm. Bull. 1999; 22: 870
    • 8b Yoshikawa M, Ueda T, Shimoda H, Murakami T, Yamahara J, Matsuda H. Chem. Pharm. Bull. 1999; 47: 383
    • 8c Yasuda T, Kayaba S, Takahashi K, Nakazawa T, Ohsawa K. J. Nat. Prod. 2004; 67: 1604
    • 8d Miyatake-Ondozabal H, Barrett AG. M. Tetrahedron Lett. 2013; 54: 4817
  • 9 For a synthetic approach to thunberginol A (2a), see: Uchiyama M, Ozawa H, Takuma K, Matsumoto Y, Yonehara M, Hiroya K, Sakamoto T. Org. Lett. 2006; 8: 5517
    • 10a Costa SS, De Souza M.deL. M, Ibrahim T, de Melo GO, de Almeida AP, Guette C, Férézou J.-P, Koatz VL. G. J. Nat. Prod. 2006; 69: 815
    • 10b Hamdache A, Lamarti A, Aleu J, Collado IG. J. Nat. Prod. 2011; 74: 893 ; and references therein
  • 11 For an excellent chapter, see: Hart H. In The Chemistry of Triple-Bonded Functional Groups . Suppl. C2 Patai S., Wiley; Chichester: 1994: Chap. 18, 1017

    • For the use of 3-alkenylcyclohex-2-en-1-ones in organic synthesis, see:
    • 12a Tissot M, Poggiali D, Hénon H, Müller D, Guénée L, Mauduit M, Alexakis A. Chem. Eur. J. 2012; 18: 8731
    • 12b Nicolaou KC, Peng X.-S, Sun Y.-P, Polet D, Zou B, Lim CS, Chen DY.-K. J. Am. Chem. Soc. 2009; 131: 10587
    • 12c Brummond KM, Chen D, Davis MM. J. Org. Chem. 2008; 73: 5064
    • 12d Brummond KM, Gao D. Org. Lett. 2003; 5: 3491
    • 13a Stork G, Danheiser RL. J. Org. Chem. 1973; 38: 1775
    • 13b Bisai A, West SP, Sarpong R. J. Am. Chem. Soc. 2008; 130: 7222
    • 13c West SP, Bisai A, Lim AD, Narayan RR, Sarpong R. J. Am. Chem. Soc. 2009; 131: 11187
    • 13d Bisai V, Sarpong R. Org. Lett. 2010; 12: 2551
    • 13e Bennett NB, Hong AY, Harned AM, Stoltz BM. Org. Biomol. Chem. 2012; 10: 56
    • 13f Kakde BN, Bhunia S, Bisai A. Tetrahedron Lett. 2013; 54: 1436
  • 14 For the synthesis of 4a, see: Smith III AB, Dorsey BD, Ohba M, Lupo AT. Jr, Malamas MS. J. Org. Chem. 1988; 53: 4314
  • 15 In 2006, Uchiyama and co-workers reported at synthesis of thunberginol A (2a) through cyclization of a carboxylic acid to a carbon–carbon triple bond in the presence of TfOH (1 equiv); see ref. 9.

    • For Bi(OTf)3-catalyzed Friedel–Crafts reactions from our group, see:
    • 16a Ghosh S, Kinthada LK, Bhunia S, Bisai A. Chem. Commun. 2012; 48: 10132
    • 16b Kinthada LK, Ghosh S, De S, Bhunia S, Dey D, Bisai A. Org. Biomol. Chem. 2013; 11: 6984
    • 16c Kakde BN, De S, Dey D, Bisai A. RSC Adv. 2013; 3: 8176
    • 16d Kinthada LK, Ghosh S, Babu KN, Sharique M, Biswas S, Bisai A. Org. Biomol. Chem. 2014; 12: 8152

      For 6-endo-dig processes on carbon–carbon triple-bond functionality, see:
    • 17a [Pd(OAc)2-catalyzed]: Wang F, Miao Z, Chen R. Org. Biomol. Chem. 2009; 7: 2848
    • 17b [CpRuCl(Ph3P)2-catalyzed]: Varela-Fernández A, González-Rodríguez C, Varela JA, Castedo L, Saá C. Org. Lett. 2009; 11: 5350
    • 17c [PPh3AuNTf2-catalyzed]: Wang X, Dong S, Yao Z, Feng L, Daka P, Wang H, Xu Z. Org. Lett. 2014; 16: 22 ; and references cited therein
    • 18a Corey EJ, Bakshi R, Shibata S, Chen CP, Singh VK. J. Am. Chem. Soc. 1987; 109: 7925
    • 18b Corey EJ, Link JO. J. Am. Chem. Soc. 1992; 114: 1906