Organocatalytic Enantioselective
Approach to the Synthesis of Verbalactone and (R)-Massoialactone

Anand Harbindu; Pradeep Kumar

doi:10.1055/s-0030-1260051

PAPER

Organocatalytic Enantioselective Approach to the Synthesis of Verbalactone and (R)-Massoialactone

Anand Harbindu, Pradeep Kumar*
Division of Organic Chemistry, National Chemical Laboratory, Pune 411008, India
Fax: +91(20)25902629; e-Mail: pk.tripathi@ncl.res.in;

Abstract

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Abstract

The organocatalytic enantioselective synthesis of verbalactone and (R)-massoialactone is described. The requisite stereogenic centers of the target molecules were constructed using l-proline-catalyzed α-aminoxylation and Horner-Wadsworth-Emmons (HWE) olefination. Yamaguchi macrolactonization and ring-closing metathesis were employed as key steps in the syntheses.

Key words

l-proline - α-aminoxylation - Horner-Wadsworth-Emmons olefination - Yamaguchi macrolactonization - ring-closing metathesis - verbalactone - massoialactone

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References

1 Magiatis P. Spanakis D. Mitaku S. Tsitsa E. Mentis A. Harvala C. J. Nat. Prod. 2001, 64: 1093

2a Gogoi S. Barua NC. Kalita B. Tetrahedron Lett. 2004, 45: 5577

2b Sharma GVM. Reddy CG. Tetrahedron Lett. 2004, 45: 7483

2c Allais F. Louvel MC. Cossy J. Synlett 2007, 451

2d Sabitha G. Bhaskar V. Yadav JS. Synth. Commun. 2008, 38: 3129

2e Wu JZ. Gao J. Ren GB. Zhen ZB. Zhang YH. Wu YK. Tetrahedron 2009, 65: 289

2f Das B. Laxminarayana K. Krishnaiah M. Kumar DN. Helv. Chim. Acta 2009, 92: 1840

2g Salunke GB. Shivakumar I. Gurjar MK. Tetrahedron Lett. 2009, 50: 2048

3 Meijer ThM. Recl. Trav. Chim. Pays-Bas 1940, 59: 191

4 Crombie L. J. Chem. Soc. 1955, 2535

5 Abe S. J. Chem. Soc. Jpn. 1937, 58: 246

6 Hashizumi T. Kikuchi N. Sasaki Y. Sakata I. Agric. Biol. Chem. 1968, 32: 1306

7 Kaiser P. Lamparsky D. Tetrahedron Lett. 1976, 1659

8 Cavill GWK. Clark DV. Whitefield FB. Aust. J. Chem. 1968, 21: 2819

9a Asaoka M. Hayashibe S. Sonoda S. Takei H. Tetrahedron Lett. 1990, 31: 4761

9b Bennett F. Knight DW. Fenton G. Heterocycles 1989, 29: 639

9c Bonini C. Pucci P. Racioppi R. Viggiani L. Tetrahedron: Asymmetry 1992, 3: 29

9d Fournier L. Gaudel-Siri A. Kocieński PJ. Pons J.-M. Synlett 2003, 107

9e Fournier L. Kocieński P. J. Pons J.-M. Tetrahedron 2004, 60: 1659

9f Gupta P. Naidu SV. Kumar P. Tetrahedron Lett. 2004, 45: 849

9g Pais GCG. Fernandes RA. Kumar P. Tetrahedron 1999, 55: 13445

9h Sabitha G. Gopal P. Yadav JS. Synth. Commun. 2007, 37: 1495

9i Touati R. Ratovelomanana-Vidal V. Ben Hassine B. Genet JP. Tetrahedron: Asymmetry 2006, 17: 3400

9j Mori K. Agric. Biol. Chem. 1976, 40: 1617

10a Harbindu A. Kumar P. Synthesis 2010, 1479

10b Kumar P. Naidu SV. Gupta P. J. Org. Chem. 2005, 70: 2843

10c Kumar P. Naidu SV. J. Org. Chem. 2005, 70: 4207

10d Gupta P. Naidu SV. Kumar P. Tetrahedron Lett. 2005, 46: 6571

10e Kumar P. Gupta P. Naidu SV. Chem. Eur. J. 2006, 12: 1397

10f Kumar P. Naidu SV. J. Org. Chem. 2006, 71: 3935

10g Gupta P. Kumar P. Eur. J. Org. Chem. 2008, 1195

10h Chowdhury PS. Gupta P. Kumar P. Tetrahedron Lett. 2009, 50: 7018

10i Kumar P. Pandey M. Gupta P. Naidu SV. Dhavale DD. Eur. J. Org. Chem. 2010, 6993

11 Kondekar NB. Kumar P. Org. Lett. 2009, 11: 2611

12

The enantiomeric excess(ee) of 7 was determined by derivatizing its precursor α,β-unsaturated γ-hydroxy ester with Mosher’s acid and analyzing the ^¹9F NMR spectrum. The ee was found to be >97%.

13 Wood NF. Chang FC. J. Org. Chem. 1965, 30: 2054