The First Total Synthesis of Pectinolide F

Abstract

The first total synthesis of the natural saturated α-pyrone pectinolide F has been accomplished from inexpensive, commercially available (S)-ethyl lactate and but-3-yn-1-ol. The salient features of the synthesis are 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO)–[bis(acetoxy)iodo]benzene oxidation, Sharpless asymmetric dihydroxylation, Grignard reaction, and partial hydrogenation of the triple bond.

Key words

pectinolide F - δ-lactones - Grignard reaction - Lindlar’s catalyst - total synthesis

• References

• 1 Pereda-Miranda R, Hernández L, Villavicencio MJ, Novelo M, Ibarra M, Chai H, Pezzuto JM. J. Nat. Prod. 1993; 56: 583
• 2 Boalino DN, Conolly JD, McLean S, Reynolds WF, Tinto WF. Phytochemistry 2003; 64: 1303
• 3 Fragoso-Serrano M, Gibbons S, Pereda-Miranda R. Planta Med. 2005; 71: 278
• 4 Mattinez M. Las Plantas Medicinales de Mexico. Editorial Botas; Mexico: 1989: 508-517
• 5 Malan K, Pelissier Y, Marion C, Blaise A, Bessiere JM. Planta Med. 1988; 54: 531

For our recent contributions to δ-lactone-containing natural products, see:
• 6a Sabitha G, Sandeep A, Rao AS, Yadav JS. Eur. J. Org. Chem. 2013; 6702
• 6b Sabitha G, Rao AS, Sandeep A, Yadav JS. Eur. J. Org. Chem. 2014; 455
• 6c Sabitha G, Shankaraiah K, Yadav JS. Eur. J. Org. Chem. 2013; 4870
• 6d Sabitha G, Reddy DV, Reddy SS. S, Yadav JS, Kumar CG, Sujitha P. RSC Adv. 2012; 2: 7241
• 6e Sabitha G, Reddy SS. S, Yadav JS. Tetrahedron Lett. 2011; 52: 2407
• 6f Sabitha G, Reddy SS. S, Raju A, Yadav JS. Synthesis 2011; 1279
• 6g Sabitha G, Reddy CN, Raju A, Yadav JS. Tetrahedron: Asymmetry 2011; 22: 493
• 6h Sabitha G, Reddy CN, Gopal P, Yadav JS. Tetrahedron Lett. 2010; 51: 5736
• 6i Sabitha G, Bhikshapathi M, Ranjith N, Ashwini N, Yadav JS. Synthesis 2011; 821
• 7 Sabitha G, Das SK, Praveen A, Yadav JS. Tetrahedron Lett. 2013; 54: 1097
• 8 Sabitha G, Praveen A, Das SK, Yadav JS. Synthesis 2013; 45: 651
• 9 Murga J, Garcia-Fortanet J, Carda M, Marco JA. Tetrahedron Lett. 2003; 44: 1737
• 10 Katsuki T, Sharpless KB. J. Am. Chem. Soc. 1980; 102: 5974
• 11 Sabitha G, Gurumurthy Ch, Yadav JS. Synthesis 2014; 46: 110
• 12a Chandrasekhar S, Sudhakar A. Org. Lett. 2010; 12: 236
• 12b The diastereomeric excess of the product was determined by using a Shimadzu high-performance liquid-chromatography (HPLC) system equipped with a chiral HPLC column (Chiralcel OD) and a UV detector at an absorbance of 225 nm. A ZORBAX SBC 18 250 - 4.6 mm, 5l (column) and a solvent system of MeCN–H₂O (4:6) at a flow rate of 1.0 mL/min were used; t_R = 6.4 and 7.1 min.
• 13 Prasad KR, Phaneendra G. Tetrahedron 2012; 68: 7489
• 14 Hansen TM, Florence GJ, Lugo-Mas P, Chen J, Abrams JN, Forsyth CJ. Tetrahedron Lett. 2003; 44: 57
• 15 Nakamura Y, Okada M, Sato A, Horikawa H, Koura M, Saito A, Taguchi T. Tetrahedron 2005; 61: 5741