Total Chemoenzymatic Synthesis of (-)-3′-Methylaristeromycin

Paul Brémond; Gérard Audran; Yoann Aubin; Honoré Monti

doi:10.1055/s-2007-973889

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2007(7): 1124-1126
DOI: 10.1055/s-2007-973889

LETTER

Total Chemoenzymatic Synthesis of (-)-3′-Methylaristeromycin

Paul Brémond, Gérard Audran*, Yoann Aubin, Honoré Monti
Laboratoire de Réactivité Organique Sélective, U.M.R. 6180 ‘Chirotechnologies: catalyse et biocatalyse’, Université Paul Cézanne, Aix-Marseille III, 13397 Marseille cedex 20, France
Fax: +33(4)91288862; e-Mail: g.audran@univ-cezanne.fr;

Further Information

Publication History

Received 14 February 2007
Publication Date:
13 April 2007 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

Enantiopure ethyl (1S,4R)-4-hydroxy-2-methylcyclopent-2-ene-1-carboxylate, readily obtained by enzymatic kinetic resolution of the corresponding racemic derivative, provided a convenient starting building block for an 11-step chiral preparation of (-)-3′-methylaristeromycin with 23% overall yield.

Key words

aristeromycin - nucleobases - carbocyclic nucleosides - stereoselective synthesis - enzymatic regioselectivity

References and Notes

1a Kishi T. Muroi M. Kusaka T. Nishikawa M. Kamiya K. Mizuno K. J. Chem. Soc., Chem. Commun. 1967, 852

Crossref Google Scholar
1b Kusaka T. Yamamoto H. Shibata M. Muroi M. Kishi T. Mizuko K. J. Antibiot. 1968, 21: 255

Crossref Google Scholar
1c Kishi T. Muroi M. Kusaka T. Nishikawa M. Kamiya K. Mizuno K. Chem. Pharm. Bull. 1972, 20: 940

Crossref Google Scholar
2a Ueland PM. Pharmacol. Rev. 1982, 34: 223

Crossref Google Scholar
2b De Clercq E. Biochem. Pharmacol. 1987, 36: 2567

Crossref Google Scholar
2c Cools M. De Clercq E. Biochem. Pharmacol. 1989, 38: 1061

Crossref Google Scholar
2d De Clercq E. Nucleosides Nucleotides 1998, 17: 625

Crossref Google Scholar
2e De Clerq E. Nucleosides, Nucleotides Nucleic Acids 2005, 24: 1395

Crossref Google Scholar
3a Bennet LL. Brockman RW. Rose LM. Allan PW. Shaddix SC. Shealy YF. Clayton JD. Mol. Pharmacol. 1985, 27: 666

Crossref Google Scholar
3b Wolfe MS. Borchardt RT. J. Med. Chem. 1991, 34: 1521

Crossref Google Scholar
4 2′-Methylaristeromycin: Gosselin G. Griffe L. Meillon J.-C. Storer R. Tetrahedron 2006, 62: 906

Crossref Google Scholar
4′-Methylaristeromycin:
5a Wachtmeister J. Mühlman A. Classon B. Samuelsson B. Tetrahedron 1999, 55: 10761

Crossref Google Scholar
5b Gumina G. Chong Y. Choi Y. Chu CK. Org. Lett. 2000, 2: 1229

Crossref Google Scholar
5c Yin X.-q. Schneller SW. Tetrahedron Lett. 2006, 47: 4057

Crossref Google Scholar
6 5′-Methylaristeromycin: Ye W. Schneller SW. J. Org. Chem. 2006, 71: 8641

Crossref Google Scholar
7 Franchetti P. Cappellacci L. Pasqualini M. Petrelli R. Vita P. Jayaram HN. Horvath Z. Szekerers T. Grifantini M. J. Med. Chem. 2005, 48: 4983

Crossref Google Scholar
8 Aubin Y. Audran G. Monti H. Synlett 2006, 2215

Article in Thieme Connect Google Scholar
9 Audran G. Acherar S. Monti H. Eur. J. Org. Chem. 2003, 92

Crossref Google Scholar
10 Corey EJ. Venkateswarlu A. J. Am. Chem. Soc. 1972, 94: 6190

Crossref Google Scholar
For some rationalizations of OsO₄ selectivity, see:
11a Poli G. Tetrahedron Lett. 1989, 30: 7385

Crossref Google Scholar
11b Katagiri N. Ito Y. Kitano K. Toyota A. Konoko C. Chem. Pharm. Bull. 1994, 42: 2653

Crossref Google Scholar
11c Ward SE. Holmes AB. McCague R. Chem. Commun. 1997, 2085

Crossref Google Scholar
Some recent selected examples and references cited therein:
12a Trost BM. Madsen R. Guile SD. Brown B. J. Am. Chem. Soc. 2000, 122: 5947

Crossref Google Scholar
12b Brown B. Hegedus LS. J. Org. Chem. 2000, 65: 1865

Crossref Google Scholar
12c Donohoe TJ. Blades K. Moore PR. Waring MJ. Winter JJG. Helliwell M. Newcombe NJ. Stemp G. J. Org. Chem. 2002, 67: 7946

Crossref Google Scholar
12d Li F. Brogan JB. Gage JL. Zhang D. Miller MJ. J. Org. Chem. 2004, 69: 4538

Crossref Google Scholar
12e Ainai T. Wang Y.-G. Tokoro Y. Kobayashi Y. J. Org. Chem. 2004, 69: 655

Crossref Google Scholar
12f Jiang MX.-W. Jin B. Gage JL. Priour A. Savela G. Miller MJ. J. Org. Chem. 2006, 71: 4164

Crossref Google Scholar
13a Mitsunobu O. Synthesis 1981, 1

Crossref Google Scholar
13b Jenny TF. Horlacher J. Previsani N. Benner SA. Helv. Chim. Acta 1992, 75: 1944

Crossref Google Scholar
13c Review: Hughes DL. Org. Prep. Proced. Int. 1996, 28: 127

Crossref Google Scholar
14 Griffith WP. Ley SV. Aldrichimica Acta 1990, 23: 13

Google Scholar
15a Kazimierczuk Z. Revankar GR. Robins RK. Nucleic Acids Res. 1984, 12: 1179

Crossref Google Scholar
15b Kazimierczuk Z. Cottam HB. Revankar GR. Robins RK. J. Am. Chem. Soc. 1984, 106: 6379

Crossref Google Scholar
18a Crimmins MT. Tetrahedron 1998, 54: 9229

Crossref Google Scholar
18b Ferrero M. Gotor V. Chem. Rev. 2000, 100: 4319

Crossref Google Scholar
18c Zhu XF. Nucleosides, Nucleotides Nucleic Acids 2000, 19: 651

Crossref Google Scholar
18d Rodriguez JB. Comin MJ. Mini-Rev. Med. Chem. 2003, 3: 95

Crossref Google Scholar
19a Lott WB. Chagovetz AM. Grissom CB. J. Am. Chem. Soc. 1995, 117: 12194

Crossref Google Scholar
19b Shuto S. Shirato M. Sumita Y. Ueno Y. Matsuda A. J. Org. Chem. 1998, 63: 1986

Crossref Google Scholar
19c Fukuoka M. Shuto S. Minakawa N. Ueno Y. Matsuda A. Tetrahedron Lett. 1999, 40: 5361

Crossref Google Scholar

16

9-[(1′ R ,2′ S ,3′ R ,4′ R )-4′-Acetoxymethyl-2′,3′- O -isopropyl-idene-3′-methylcyclopent-1′-yl]adenine [(-)-11]: To a stirred solution of adenine (476 mg, 3.52 mmol, 2.5 equiv) in DMF (30 mL) at 0 °C under an argon atmosphere was added NaH (113 mg, 2.82 mmol, 2.0 equiv, 60% dispersion in mineral oil). The reaction mixture was heated to 60 °C and stirred at this temperature for 2 h. After cooling the solution to 0 °C, triflate (-)-10 (530 mg, 1.41 mmol) in DMF (3 mL) was added dropwise. After stirring for 2 h at 60 °C, the reaction mixture was concentrated in vacuo, and the residue was purified by column chromatography (CH₂Cl₂-MeOH) to give compound (-)-11 (380 mg, 75%) as a foam.

17

Characterization of selected new compounds:
Compound (+)-5: oil; [α]²⁵ _D +31.7 (c = 1.0, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 4.12-4.23 (m, 3 H), 3.94 (d, J = 1.8 Hz, 1 H), 2.95 (dd, J = 7.1, 11.3 Hz, 1 H), 2.32 (dt, J = 7.1, 13.6 Hz, 1 H), 2.06 (ddd, J = 7.1, 11.3, 13.6 Hz, 1 H), 1.49 (s, 3 H), 1.40 (s, 3 H), 1.35 (s, 3 H), 1.27 (t, J = 7.2 Hz, 3 H), 0.88 (s, 9 H), 0.08 (s, 3 H), 0.07 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 172.2 (C), 112.0 (C), 93.5 (CH), 88.5 (C), 74.8 (CH), 60.5 (CH₂), 53.3 (CH), 36.8 (CH₂), 28.3 (Me), 26.8 (Me), 25.7 (3 × Me), 21.7 (Me), 17.9 (C), 14.3 (Me), 4.9 (Me), 5.0 (Me). Anal. Calcd for C₁₈H₃₄O₅Si: C, 60.30; H, 9.56. Found: C, 60.19; H 9.59.
Compound (-)-10: white needles; mp 59-60 °C; [α]²⁵ _D -32.1 (c = 1.0, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 5.13 (ddd, J = 5.6, 7.0, 8.8 Hz, 1 H), 4.32 (d, J = 5.6 Hz, 1 H), 4.06, 4.00 (ABX, J = 4.8, 5.0, 11.6 Hz, 2 H), 2.50 (dt, J = 8.8, 12.5 Hz, 1 H), 2.38-2.44 (m, 1 H), 2.05 (s, 3 H), 1.98-2.05 (m partially overlapped, 1 H), 1.46 (s, 3 H), 1.42 (s, 3 H), 1.41 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 170.3 (C), 118.5 (q, J = 317 Hz, CF₃), 113.1 (C), 89.2 (C), 85.2 (CH), 84.4 (CH), 63.7 (CH₂), 44.2 (CH), 32.9 (CH₂), 27.6 (Me), 27.5 (Me), 21.6 (Me), 20.7 (Me). Anal. Calcd for C₁₃H₁₉F₃O₇S: C, 41.49; H, 5.09. Found: C, 41.73; H 5.13.
Compound (-)-11: [α]²⁵ _D -15.7 (c = 1.0, MeOH). ¹H NMR (300 MHz, DMSO-d ₆): δ = 8.26 (s, 1 H), 8.15 (s, 1 H), 7.26 (br s, 2 H), 4.91 (dt, J = 3.7, 9.5 Hz, 1 H), 4.51 (d, J = 3.7 Hz, 1 H), 4.12 (d, J = 6.8 Hz, 2 H), 2.40-2.46 (m, 1 H), 2.30-2.37 (m, 2 H), 2.01 (s, 3 H), 1.53 (s, 3 H), 1.46 (s, 3 H), 1.26 (s, 3 H). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 170.4 (C), 156.1 (C), 152.4 (CH), 149.3 (C), 140.0 (CH), 119.3 (C), 112.8 (C), 90.4 (CH), 87.6 (C), 62.8 (CH₂), 58.4 (CH), 46.6 (CH), 34.0 (CH₂), 28.6 (Me), 27.2 (Me), 20.7 (Me), 20.5 (Me). Anal. Calcd for C₁₇H₂₃N₅O₄: C, 56.50; H, 6.41; N, 19.38. Found: C, 56.19; H, 6.37; N, 19.59.
Compound (-)-1: white solid; mp 146-147 °C; [α]²⁵ _D -10.5 (c = 1.0, MeOH). ¹H NMR (500 MHz, CD₃OD): δ = 8.22 (s, 1 H), 8.18 (s, 1 H), 4.87 (q, partially overlapped with HDO, J = 9.6 Hz, 1 H), 4.34 (d, J = 9.6 Hz, 1 H), 3.75 (d, J = 4.8 Hz, 2 H), 2.62 (dt, J = 9.6, 13.8 Hz, 1 H), 2.17 (dq, J = 4.8, 9.6 Hz, 1 H), 2.05 (ddd, J = 4.8, 9.6, 13.8 Hz, 1 H), 1.36 (s, 3 H). ¹³C NMR (125 MHz, CD₃OD): δ = 157.1 (C), 152.9 (CH), 150.7 (C), 142.3 (CH), 120.6 (C), 81.1 (CH), 78.8 (C), 63.9 (CH₂), 61.6 (CH), 48.7 (CH), 30.3 (CH₂), 21.6 (Me). Anal. Calcd for C₁₂H₁₇O₃N₅: C, 51.60; H, 6.13; N, 25.07. Found: C, 51.99; H, 6.09; N, 24.79.