Total Synthesis of Laingolide A Diastereomers

Gaétan Pomey; Phannarath Phansavath

doi:10.1055/s-0034-1380133

Synthesis, Table of Contents

Synthesis 2015; 47(07): 1016-1023
DOI: 10.1055/s-0034-1380133

paper

Total Synthesis of Laingolide A Diastereomers

Gaétan Pomey

PSL Research University, Chimie ParisTech-CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France Email: phannarath.phansavath@chimie-paristech.fr

,

Phannarath Phansavath*

PSL Research University, Chimie ParisTech-CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France Email: phannarath.phansavath@chimie-paristech.fr

› Author Affiliations

Abstract

All articles of this category

Abstract

The first total syntheses of two (±)-laingolide A diastereomers were achieved in 11 and 12 steps, respectively. The key steps include a tandem cross-dimerization/oxonia-Cope reaction and an intramolecular dehydrative cyclization for the formation of either the trans- or cis-enamide moieties.

Key words

natural products - total synthesis - macrocycles - ring expansion - oxonia-Cope reactions

Full Text

References

References
1 Klein D, Braekman J.-C, Daloze D, Hoffmann L, Demoulin V. Tetrahedron Lett. 1996; 37: 7519
2 Klein D, Braekman J.-C, Daloze D, Hoffmann L, Castillo G, Demoulin V. J. Nat. Prod. 1999; 62: 934
3 Matthew S, Salvador LA, Schupp PJ, Paul VJ, Luesch H. J. Nat. Prod. 2010; 73: 1544
4 Pereira AR, Cao Z, Engene N, Soria-Mercado IE, Murray TF, Gerwick WH. Org. Lett. 2010; 12: 4490

5a Tello-Aburto R, Johnson EM, Valdez CK, Maio WA. Org. Lett. 2012; 14: 2150
5b Tello-Aburto R, Newar TD, Maio WA. J. Org. Chem. 2012; 77: 6271
5c Wadsworth AD, Furkert DP, Sperry J, Brimble MA. Org. Lett. 2012; 14: 5374
5d Sudhakar G, Reddy KJ, Nanubolu JB. Tetrahedron 2013; 69: 2419
5e Philkhana SC, Seetharamsingh B, Dangat YB, Vanka K, Reddy DS. Chem. Commun. 2013; 49: 3342
5f Wadsworth AD, Furkert DP, Brimble MA. J. Org. Chem. 2014; 79: 11179

6 Mehrotra S, Duggan BM, Tello-Aburto R, Newar TD, Gerwick WH, Murray TF, Maio WA. J. Nat. Prod. 2014; 77: 2553

7a Echeverria P.-G, Prévost S, Cornil J, Férard C, Reymond S, Guérinot A, Cossy J, Ratovelomanana-Vidal V, Phansavath P. Org. Lett. 2014; 16: 2390
7b Prévost S, Ayad T, Phansavath P, Ratovelomanana-Vidal V. Adv. Synth. Catal. 2011; 353: 3213
7c Roche C, Desroy N, Haddad M, Phansavath P, Genet J.-P. Org. Lett. 2008; 10: 3911

8 Zou Y, Ding C, Zhou L, Li Z, Wang Q, Schoenebeck F, Goeke A. Angew. Chem. Int. Ed. 2012; 51: 5647

9a Huynh C, Derguini-Boumechal F, Linstrumelle G. Tetrahedron Lett. 1979; 20: 1503
9b Warrington JM, Barriault L. Org. Lett. 2005; 7: 4589

10 The relative configuration between the C(7) and C(9) stereocenters in compound 11 was assigned on the basis of NOESY experiments, and the trans relationship was later confirmed by an X-ray crystal structure analysis of the parent compound 15.
11 To ascertain that no enrichment in trans-11 at the expense of the cis-isomer occurred during the purification process, a sample of pure (Z)-10 was subjected to the hydrogenation reaction and the trans-isomer was obtained exclusively.
12 Formation of the cis-isomer can be rationalized by considering the most stable conformation of the 10-membered lactone enolate (boat–chair–boat conformation), see: Still WC, Galynker I. Tetrahedron 1981; 37: 3981
13 Epp JB, Widlanski TS. J. Org. Chem. 1999; 64: 293
14 Nakamura T, Noguchi T, Kobayashi H, Miyachi H, Hashimoto Y. Chem. Pharm. Bull. 2006; 54: 1709
15 Shea KJ, Wada E. J. Am. Chem. Soc. 1982; 104: 5715
16 Inanaga J, Hirata K, Saeki H, Katsuki T, Yamaguchi M. Bull. Chem. Soc. Jpn. 1979; 52: 1989

Supplementary Material

Supporting Information