Synthesis of Methyl Axenoside and Methyl 3-epi-Axenoside via Ate-Mediated Allylic Substitution (AMAS)

Brian A. Ondrusek; D. Tyler McQuade

doi:10.1055/s-0033-1339116

Synlett, Table of Contents

Synlett 2014; 25(11): 1547-1549
DOI: 10.1055/s-0033-1339116

letter

Synthesis of Methyl Axenoside and Methyl 3-epi-Axenoside via Ate-Mediated Allylic Substitution (AMAS)

Brian A. Ondrusek

Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL, 32306-4390, USA Fax: +1(850)6648281 Email: mcquade@chem.fsu.edu

,

D. Tyler McQuade*

Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL, 32306-4390, USA Fax: +1(850)6648281 Email: mcquade@chem.fsu.edu

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Abstract

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Abstract

An ate-mediated allylic substitution (AMAS) of vinylboronates is utilized in the divergent syntheses of the sugars methyl axenoside and methyl 3-epi-axenoside. Other key steps of the synthesis involve the dihydroxylation of the resulting allylic alcohol and selective oxidation of the resultant diol. Benefits of this methodology are also discussed.

Key words

asymmetric synthesis - boron - homogeneous catalysis - natural products - total synthesis

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References

References and Notes

Axenomycin:

1a Arcamone F, Barbieri W, Franceschi G, Penco S, Vigevani A. J. Am. Chem. Soc. 1973; 95: 2008

Polyketomycin:

1b Momose I, Chen W, Kinoshita N, Iinuma H, Hamada M, Takeuchi T. J. Antibiot. 1998; 51: 21
1c Momose I, Chen W, Kinoshita N, Iinuma H, Hamada M, Takeuchi T. J. Antibiot. 1998; 51: 26
1d Micalizzi DS, Dougherty JP, Noecker LA, Smith GR, Giuliano RM. Tetrahedron: Asymmetry 2003; 14: 3183

Dutomycin:

1e Xuan L.-J, Xu S.-H, Zhang H.-L, Xu Y.-M. J. Antibiot. 1992; 45: 1974

2 Garegg PJ, Norberg T. Acta Chem. Scand. B 1975; 29: 507
3 Smith GR, Villani FJ. Jr, Failli L, Giuliano RM. Tetrahedron: Asymmetry 2000; 11: 139

For other de novo syntheses of deoxy sugars, see:

4a Ahmed MdM, Berry BP, Hunter TJ, Tomcik DJ, O’Doherty GA. Org. Lett. 2005; 7: 745
4b Ahmed MdM, O’Doherty GA. Tetrahedron Lett. 2005; 46: 3015
4c Ahmed MdM, O’Doherty GA. Carbohydrate Res. 2006; 341: 1505

5 Smaltz DJ, Švenda J, Myers AG. Org. Lett. 2012; 14: 1812
6 Park JK, Ondrusek BA. McQuade D. T. Org. Lett. 2012; 14: 4790
7 Ondrusek BA, Park JK, McQuade DT. Synlett 2014; 25: 239
8 See Supporting Information for a discussion on unsuccessful methodologies. All compounds not found in the article will be numbered sequentially beginning with 17.
9 Kolb HC, VanNieuwenhze MS, Sharpless KB. Chem. Rev. 1994; 94: 2483

For references on the dihydroxylation of alkenes bearing allylic heteroatoms, see:

10a Donohoe TJ, Moore PR, Waring MJ. Tetrahedron Lett. 1997; 38: 5027
10b Kallatsa OA, Koskinen AM. P. Tetrahedron Lett. 1997; 38: 8895
10c Donohoe TJ, Blades K, Helliwell M, Moore PR, Winter JJ. G. J. Org. Chem. 1999; 64: 2980
10d Blades K, Donohoe TJ, Winter JJ. G, Stemp G. Tetrahedron Lett. 2000; 41: 4701
10e Donohoe TJ, Blades K, Moore PR, Waring MJ, Winter JJ. G, Helliwell M, Newcombe NJ, Stemp G. J. Org. Chem. 2002; 67: 7946

11 See Supporting Information for additional procedural information.
12 Sharif EU, Wang H.-YL, Akhmedov NG, O’Doherty GA. Org. Lett. 2014; 16: 492
13 See Supporting Information for a discussion on unsuccessful strategies toward acetonide deprotection–cyclization.
14 Kobayashi S, Reddy RS, Sugiura Y, Sasaki D, Miyagawa N, Hirama M. J. Am. Chem. Soc. 2001; 123: 2887
15 The Myers group⁴ suggests that these α/β ratios are a thermodynamic mixture.

Supplementary Material

Supporting Information