Stereocontrolled Synthesis of C-Arylglycosides Applied to the South West Fragment of the Antibiotic Kendomycin

Abstract

A nine step synthesis of the southwest fragment 3 of the antibiotic kendomycin (1) is reported. The tetrahydropyran ring is prepared in a highly stereocontrolled and efficient sequence. The key step concerns an anti-aldol reaction using chiral ketone 10. C-Aryl glycoside 3 exhibits atropisomerism and the relative configuration around its tetrahydropyran ring was established by NOE experiments.

total synthesis - natural products - aldol reactions - glycosides - atropisomerism - antibiotics

References

1a Funahashi Y, Kawamura N, and Ishimaru T. inventors; Jap. Pat.  08231551 [A2960910].  ; Chem. Abstr. 1997, 126, 6553

1b Funahashi N, and Kawamura N. inventors; Jap. Pat.  08231552 [A2960910].  ; Chem. Abstr. 1996, 125, 326518

1c Su MH, Hosken MI, Hotovec BJ, and Johnston TL. inventors; US Pat.  5728727 [A980317].  ; Chem. Abstr. 1998, 128, 239489

2a Bode HB. Zeeck A. J. Chem. Soc., Perkin Trans. 1  2000,  323 

2b Bode HB. Zeeck A. J. Chem. Soc., Perkin Trans. 1  2000,  2665 

3 Martin HJ. Drescher M. Kählig H. Schneider S. Mulzer J. Angew. Chem. Int. Ed.  2001,  40:  3186 

4 For a review about how to make C-aryl glycosides, see: Jaramillo C. Knapp S. Synthesis  1994,  1 

5 Rieche A. Gross H. Hoft E. Chem. Ber.  1960,  93:  88 

6 Lee CS. Forsyth CJ. Tetrahedron Lett.  1996,  37:  6449 

7 Cowden CJ. Paterson I. Org. React.  1997,  51:  1 

8 Evans DA. Ng HP. Clark JS. Rieger DL. Tetrahedron  1992,  48:  2127 

9 Maruyama K. Nagai N. Naruta Y. J. Org. Chem.  1986,  51:  5083 

10 Carreno MC. Ruano JLG. Sanz G. Toledo MA. Urbano A. J. Org. Chem.  1995,  60:  5328