First Stereoselective Total Synthesis of Cryptomoscatone D2 and Syntheses of (5R,7S)-Kurzilactone and (+)-Cryptofolione by an Asymmetric Acetate Aldol Approach

Abstract

An efficient concise stereoselective total synthesis of cryptomoscatone D2 and syntheses of (5R,7S)-kurzilactone and (+)-cryptofolione, based on an asymmetric acetate aldol reaction starting from trans-cinnamaldehyde, are described. The other key reactions are a Horner–Wadsworth–Emmons reaction, a Brown’s asymmetric allylation and a ring-closing metathesis.

Key words

lactones - stereoselective synthesis - total synthesis - aldol reactions - cyclizations

• References

• 1 Sehlapelo BM, Drewes SE, Scott-Shaw R. Phytochemistry 1994; 37: 847
• 2 Cavalheiro AJ, Yoshida M. Phytochemistry 2000; 53: 811
• 3 Nehme CJ, Bastos WL, De Araujo AJ, Cavalheiro AJ. Phytochem. Anal. 2005; 16: 93
• 4 Drewes SE, Horn MH, Mavi S. Phytochemistry 1997; 44: 437
• 5 Zschocke S, van Staden J. J. Ethnopharmacol. 2000; 71: 473
• 6a Hawariah A, Stanslas J. Anticancer Res. 1998; 18: 4383
• 6b Pihie AH. L, Stanslas J, Din LB. Anticancer Res. 1998; 18: 1739
• 6c Ee YS, Lai LC, Reimann K, Lim PK. Oncol. Rep. 1999; 6: 843
• 7 Giocondo MP, Bassi CL, Telascrea M, Cavalheiro AJ, Bolzani VS, Silva DH. S, Agustoni D, Mello ER, Soares CP. Rev. Cienc. Farm. Basica Apl. 2009; 30: 315
• 8 Sturgeon CM, Cinel B, Díaz-Marrero AR, McHardy LM, Ngo M, Andersen RJ, Roberge M. Cancer Chemother. Pharmacol. 2008; 61: 407
• 9 Fu X, Sevenet T, Hamid A, Hadi A, Remy F, Pais M. Phytochemistry 1993; 33: 1272
• 10 Schmeda-Hirschmann G, Astudillo L, Bastida J, Codina C, Rojas De Arias A, Ferreira ME, Inchaustti A, Yaluff G. J. Pharm. Pharmacol. 2001; 53: 563
• 11a Matsuoka Y, Aikawa K, Irie R, Katsuki T. Heterocycles 2005; 66: 187
• 11b Sabitha G, Reddy SS. S, Reddy DV, Bhaskar V, Yadav JS. Synthesis 2010; 3453
• 11c Kumar RN, Meshram HM. Tetrahedron Lett. 2011; 52: 1003
• 11d Das B, Nagendra S, Reddy CR. Tetrahedron: Asymmetry 2011; 22: 1249
• 12a Jiang B, Chen Z. Tetrahedron: Asymmetry 2001; 12: 2835
• 12b Kim Y-J, Tae J. Synlett 2006; 61
• 12c Sabitha G, Gopal P, Reddy CN, Yadav JS. Synthesis 2009; 3301

• For our contributions on lactone-containing molecules, see:

• 13a Yadav JS, Mandal SS. Tetrahedron Lett. 2011; 52: 5747
• 13b Yadav JS, Mandal SS, Reddy JS. S, Srihari P. Tetrahedron 2011; 67: 4620
• 13c Yadav JS, Reddy JS. S, Mandal SS, Srihari P. Synlett 2010; 2636
• 13d Srihari P, Kumaraswamy B, Rao GM, Yadav JS. Tetrahedron: Asymmetry 2010; 21: 106
• 13e Srihari P, Bhasker EV, Reddy AB, Yadav JS. Tetrahedron Lett. 2009; 50: 2420
• 13f Yadav JS, Kumar VN, Rao RS, Srihari P. Synthesis 2008; 1938
• 13g Srihari P, Kumar BP, Subbarayudu K, Yadav JS. Tetrahedron Lett. 2007; 48: 6977
• 13h Srihari P, Bhasker EV, Harshavardhan SJ, Yadav JS. Synthesis 2006; 4041

• For the synthesis of the N-acetylthiazolidinethione complex, see:

• 14a Crimmins MT, Chaudhary K. Org. Lett. 2000; 2: 775
• 14b Yadav JS, Kumar VN, Rao RS, Srihari P. Synthesis 2008; 1938

Procedures for the syn aldol reaction were adapted from:
• 14c Hodge MB, Olivo HF. Tetrahedron 2004; 60: 9397
• 14d Crimmins MT, King BW, Tabet EA, Chaudhary K. J. Org. Chem. 2001; 66: 894
• 14e Srihari P, Satyanarayana K, Ganganna B, Yadav JS. J. Org. Chem. 2011; 76: 1922

For the generation of 1,3-diol units with anti-geometry, see:
• 14f Evans DA, Chapman KT, Carreira EM. J. Am. Chem. Soc. 1988; 110: 3560
• 14g Labeeuw O, Roche C, Phansavath P, Genêt J.-P. Org. Lett. 2007; 9: 105
• 14h Kondekar NB, Kumar P. Org. Lett. 2009; 11: 2611
• 14i Hassan A, Lu Y, Krische MJ. Org. Lett. 2009; 11: 3112
• 15a Brown HC, Jadhav PK. J. Am. Chem. Soc. 1983; 105: 2092
• 15b Brown HC, Jadhav PK. J. Org. Chem. 1984; 49: 4089
• 15c Brown HC, Jadhav PK, Bhat KS, Perumal PT. J. Org. Chem. 1986; 51: 432
• 15d Brown HC, Bhat KS, Randad RS. J. Org. Chem. 1987; 52: 319
• 15e Brown HC, Bhat KS, Randad RS. J. Org. Chem. 1989; 54: 1570
• 15f Brown HC, Randad RS, Bhat KS, Zaidlewicz M, Racherla US. J. Am. Chem. Soc. 1990; 112: 2389
• 16 The presence of a single diastereomer was confirmed by ¹H and ¹³C NMR analysis
• 17a Grubbs RH, Chang S. Tetrahedron 1998; 54: 4413
• 17b Grubbs RH. Tetrahedron 2004; 60: 7117
• 17c Furstner A. Angew. Chem. Int. Ed. 2000; 39: 3012
• 17d Trnka TM, Grubbs RH. Acc. Chem. Res. 2001; 34: 18
• 18 Etayo P, Badorrey R, Díaz-de-Villegas MD, Gálvez JA. J. Org. Chem. 2007; 72: 1005
• 19 Compound 21 was prepared in three steps from bromoacetyl bromide according to the reported method; see: Nuzillard J.-M, Boumendjel A, Massiot G. Tetrahedron Lett. 1989; 30: 3779