Asymmetric Synthesis of 2,4,6-Trideoxy-4-(dimethylamino)-3-C-methyl-l-lyxohexopyranose
(Lemonose)

Guillaume Bernadat; Nicolas George; Cédric Couturier; Géraldine Masson; Thierry Schlama; Jieping Zhu

doi:10.1055/s-0030-1259531

LETTER

Asymmetric Synthesis of 2,4,6-Trideoxy-4-(dimethylamino)-3-C-methyl-l-lyxohexopyranose (Lemonose)

Guillaume Bernadat^a, Nicolas George^a, Cédric Couturier^a, Géraldine Masson*^a, Thierry Schlama^b, Jieping Zhu*^a,c
^a Centre de Recherche de Gif, Institut de Chimie des Substances Naturelles, CNRS, 91198 Gif-sur-Yvette Cedex, France
Fax: +33(1)69077247; e-Mail: geraldine.masson@icsn.cnrs-gif.fr;
^b RHODIA, Centre de Recherches et de Technologie de Lyon (CRTL), avenue des Frères Perret, BP 62, 69192 Saint-Fons Cedex, France
^c Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), EPFL-SB-ISIC-LSPN, 1015 Lausanne, Switzerland
e-Mail: jieping.zhu@epfl.ch;

Abstract

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Abstract

l-Lemonose, the glycosidic part of (-)-lemonomycin, has been synthesized in ten steps with 18% overall yield from d-threonine. The key steps are a double, highly diastereoselective Grignard addition to a Weinreb amide and a chemoselective oxidation of a primary alcohol in the presence of a secondary alcohol, a tertiary alcohol and a tertiary amine, leading directly to the lactol.

Key words

sugar - aminosugar - lemonomycin - lemonose tetrahydroisoquinoline

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References

References and Notes

1a Whaley HA. Patterson EL. Dann M. Shay AJ. Porter JN. Antimicrob. Agents Chemother. 1964, 8: 83

1b He H. Shen B. Carter GT. Tetrahedron Lett. 2000, 41: 2067

2a Scott JD. Williams RM. Chem. Rev. 2002, 102: 1669

2b Siengalewicz P. Rinner U. Mulzer J. Chem. Soc. Rev. 2008, 37: 2676

3a Constantine KL. Mueller L. Huang S. Abid S. Lam KS. Li W. Leet JE. J. Am. Chem. Soc. 2002, 124: 7284

3b Leet JE. Li W. Ax HA. Matson JA. Huang S. Huang R. Cantone JL. Drexler D. Dalterio RA. Lam KS. J. Antibiot. 2003, 56: 226

3c Leet JE. Li W. Ax HA. Matson JA. Huang S. Huang R. Cantone JL. Drexler D. Dalterio RA. Lam KS.
J. Antibiot. 2003, 56: 232

4 Sasaki T. Otani T. Matsumoto H. Unemi N. Hamada M. Takeuchi T. Hori M. J. Antibiot. 1998, 51: 715

5a Steinberg DA. Bernan VS. Montenegro DA. Abbanat DR. Pearce CJ. Korshalla JD. Jacobus NV. Petersen PJ. Mroczenski-Wildey MJ. Maiese WM. J. Antibiot. 1994, 47: 887

5b Northcote PT. Williams D. Manning JK. Borders DB. Maiese WM. Lee MD. J. Antibiot. 1994, 47: 894

5c Northcote PT. Siegel M. Borders DB. Lee MD. J. Antibiot. 1994, 47: 901

6a Horan AC. Shearer MC. Hegde V. Beyazova ML. Brodsky BC. King A. Berrie R. Cardaci K. Nimeck M. J. Antibiot. 1997, 50: 119

6b Hegde VR. Patel MG. Das PR. Pramanik B. Puar MS.
J. Antibiot. 1997, 50: 126

7 Zhang C. Herath K. Jayasuriya H. Ondeyka JG. Zink DL. Occi J. Birdsall G. Venugopal J. Ushio M. Burgess B. Masurekar P. Barrett JF. Singh SB. J. Nat. Prod. 2009, 72: 841

8 Ashley ER. Cruz EG. Stoltz BM. J. Am. Chem. Soc. 2003, 125: 15000

9 Magnus P. Matthews KS. J. Am. Chem. Soc. 2005, 127: 12476

10 Rikimaru K. Mori K. Kan T. Fukuyama T. Chem. Commun. 2005, 394

11 Vincent G. Chen Y. Lane JW. Williams RM. Heterocycles 2007, 72: 385

12 Siengalewicz P. Brecker L. Mulzer J. Synlett 2008, 2443

13a Wu Y.-C. Bernadat G. Masson G. Couturier C. Schlama T. Zhu J. J. Org. Chem. 2009, 74: 2046

13b Couturier C. Schlama T. Zhu J. Synlett 2006, 1691

For syntheses of other natural products belonging to the same family from our group, see:

14a Wu Y.-C. Liron M. Zhu J. J. Am. Chem. Soc. 2008, 130: 7148

14b Chen X. Zhu J. Angew. Chem. Int. Ed. 2007, 46: 3962

14c Chen J. Chen X. Willot M. Zhu J. Angew. Chem. Int. Ed. 2006, 45: 8028

14d Chen J. Chen X. Bois-Choussy M. Zhu J. J. Am. Chem. Soc. 2006, 128: 87

14e Chen XC. Chen JC. De Paolis M. Zhu J. J. Org. Chem. 2005, 70: 4397

15a Reetz MT. Hüllmann M. Seitz T. Angew. Chem., Int. Ed. Engl. 1987, 26: 477

15b Mengel A. Reiser O. Chem. Rev. 1999, 99: 1191

16a Maurer PJ. Knudsen CG. Palkowitz AD. Rapoport H. J. Org. Chem. 1985, 50: 325

16b Evans DA. Hu E. Tedrow JS. Org. Lett. 2001, 3: 3133

Selected conditions included:

17a

adding HMPT to capture the counter-ion;

17b

adding BF₃˙OEt₂ to pre-complex the aldehyde, and

17c

replacing LDA with KHMDS.

18a Imamoto T. Kusumoto T. Tawarayama Y. Sugiura Y. Mita T. Hatanaka Y. Yokoyama M. J. Org. Chem. 1984, 49: 3904

18b Paquette LA. In Encyclopedia of Reagents for Organic Synthesis Paquette LA. John Wiley & Sons; New York: 1995. p.1031

18c Greeves N. Lyford L. Tetrahedron Lett. 1992, 33: 4759

19 Sousa JA. Bluhm AL. J. Org. Chem. 1960, 25: 108

20 For selective oxidation of primary alcohols in the presence of secondary alcoholic groups with IBX, see: Corey EJ. Palani A. Tetrahedron Lett. 1995, 36: 3485

21a Frigerio M. Santagostino M. Sputore S. Palmisano G. J. Org. Chem. 1995, 60: 7272

21b Zhdankin VV. Stang PJ. Chem. Rev. 2002, 102: 2523

21c Richardson RD. Zayed JM. Altermann S. Smith D. Wirth T. Angew. Chem. Int. Ed. 2007, 46: 6529 ; and references cited therein

21d Moorthy JN. Singhal N. Senapati K. Org. Biomol. Chem. 2007, 5: 767

21e Moorthy JN. Singhal N. Senapati K. Tetrahedron Lett. 2008, 49: 80

22a Dess DB. Martin JC. J. Org. Chem. 1983, 48: 4155

22b Dess DB. Martin JC. J. Am. Chem. Soc. 1991, 113: 7277

22c Boeckman RK. Shao P. Mullins JJ. Org. Synth. 2000, 77: 141

23a Nicolaou KC. Mathison CJN. Montagnon T. Angew. Chem. Int. Ed. 2003, 42: 4077

23b Nicolaou KC. Mathison CJN. Montagnon T. J. Am. Chem. Soc. 2004, 126: 5192

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