Synthesis of Bistramide A and Analogues, Part 1: Stereoselective Access to Normethyl Tetrahydropyran Subunit

Marie-Aude Hiebel; Béatrice Pelotier; Paul Lhoste; Olivier Piva

doi:10.1055/s-2008-1072714

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 2008(8): 1202-1204
DOI: 10.1055/s-2008-1072714

LETTER

Synthesis of Bistramide A and Analogues, Part 1: Stereoselective Access to Normethyl Tetrahydropyran Subunit

Marie-Aude Hiebel, Béatrice Pelotier*, Paul Lhoste, Olivier Piva*
Institut de Chimie et de Biochimie Moléculaires et Supramoléculaires (ICBMS), UMR 5246, Université de Lyon 1, CNRS, 43, Bd du 11 Novembre 1918, 69622 Villeurbanne cedex, France
e-Mail: beatrice.pelotier@univ-lyon1.fr; e-Mail: piva@univ-lyon1.fr;

Further Information

Publication History

Received 24 January 2008
Publication Date:
16 April 2008 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

A stereoselective synthesis of normethyl C1-C13 fragment of bistramide A is described. The key steps involve an asymmetric Sharpless epoxidation, a cross-metathesis reaction and an intramolecular oxa-Michael reaction. The trans-2,6-disubstituted tetrahydropyran subunit has been synthesized in an overall yield of 7% with 96% ee. The cis isomer was prepared by a similar pathway with the same efficiency and enantioselectivity.

Key words

bistramide A - normethyl - Sharpless epoxidation - cross-metathesis reaction - intramolecular oxa-Michael reaction

References and Notes

1 Gouiffes D. Moreau S. Helbecque N. Bernier JL. Henichard JP. Barbin Y. Laurent D. Verbist JF. Tetrahedron 1988, 44: 451

Crossref Google Scholar
2 Biard JF. Roussakis C. Kornprobst JM. Gouiffes-Barbin D. Verbist JF. Cotelle P. Foster MP. Ireland CM. Debitus C. J. Nat. Prod. 1994, 57: 1336

Crossref Google Scholar
3 Riou D. Roussakis C. Robillard N. Biard JF. Verbist JF. Biol. Cell 1993, 77: 261

Crossref Google Scholar
4 Sauviat MP. Verbist JF. Gen. Physiol. Biophys. 1993, 12: 465

Google Scholar
5 Statsuk AV. Liu D. Kozmin SA. J. Am. Chem. Soc. 2004, 126: 9546

Crossref Google Scholar
6 Crimmins MT. DeBaillie AC. J. Am. Chem. Soc. 2006, 128: 4936

Crossref PubMed Google Scholar
7 Lowe JT. Wrona IE. Panek JS. Org. Lett. 2007, 9: 327

Crossref Google Scholar
8 Yadav JS. Chetia L. Org. Lett. 2007, 9: 4587

Crossref PubMed Google Scholar
9 Griffiths G. Garrone B. Deacon E. Owen P. Pongracz J. Mead G. Bradwell A. Watters D. Lord J. Biochem. Biophys. Res. Commun. 1996, 222: 802

Crossref Google Scholar
10a Statsuk AV. Bai R. Baryza JL. Verma VA. Hamel E. Wender PA. Kozmin SA. Nat. Chem. Biol. 2005, 1: 383

Crossref Google Scholar
10b Rizvi SA. Tereshko V. Kossiakoff AA. Kozmin SA. J. Am. Chem. Soc. 2006, 128: 3882

Crossref Google Scholar
11 Gallagher PO. McErlean CSP. Jacobs MF. Watters DJ. Kitching W. Tetrahedron Lett. 2002, 43: 531

Crossref Google Scholar
12a Wipf P. Hopkins TD. Chem. Commun. 2005, 3421

Crossref Google Scholar
12b Evans PA. Cui J. Gharpure SJ. Hinckle RJ. J. Am. Chem. Soc. 2003, 125: 11456

Crossref Google Scholar
13 Lowe JT. Panek JS. Org. Lett. 2005, 7: 3231

Crossref Google Scholar
14 Wipf P. Uto Y. Yoshimura S. Chem. Eur. J. 2002, 8: 1670

Crossref Google Scholar
15a Edmunds AJF. Trueb W. Tetrahedron Lett. 1997, 38: 1009

Crossref Google Scholar
15b MacCoss RN. Balskus EP. Ley SV. Tetrahedron Lett. 2003, 44: 7779

Crossref Google Scholar
15c McAllister GD. Oswald MF. Paxton RJ. Raw SA. Taylor RJK. Tetrahedron 2006, 62: 6681

Crossref Google Scholar
16 Katsuki T. Sharpless KB. J. Am. Chem. Soc. 1980, 102: 5974

Google Scholar
17 Crisóstomo FRP. Carrillo R. León LG. Martín T. Padrón JM. Martín VS. J. Org. Chem. 2006, 71: 2339

Crossref Google Scholar
20a Finan JM. Kishi Y. Tetrahedron Lett. 1982, 23: 2719

Google Scholar
20b Ma P. Martin VS. Masamune S. Sharpless KB. Viti SM. J. Org. Chem. 1982, 47: 1378

Google Scholar
23 Chaterjee AK. Choi T.-L. Sanders DP. Grubbs RH. J. Am. Chem. Soc. 2003, 125: 11360

Crossref Google Scholar
25 Banwell MG. Bui CT. Pham HTT. Simpson GW. J. Chem. Soc., Perkin Trans. 1 1996, 967

Crossref Google Scholar
28 Dess DB. Martin JC. J. Org. Chem. 1983, 48: 4155

Crossref Google Scholar
29 Marton D. Stivanello D. Tagliavini G. J. Org. Chem. 1996, 61: 2731

Crossref Google Scholar
30 Huang SL. Swern D. J. Org. Chem. 1978, 43: 4537

Crossref Google Scholar

18

Epoxy alcohol 2: [α]_D ²⁰ +38.8 (c = 1, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 1.54-1.58 (m, 4 H), 1.85 (br s, 1 H), 2.03-2.16 (m, 2 H), 2.91-2.95 (m, 2 H), 3.61 (dd, J = 4.1, 12.6 Hz, 1 H), 3.90 (dd, J = 2.3, 12.6 Hz, 1 H), 4.28-5.04 (m, 2 H), 5.78 (ddt, J = 6.6, 10.2, 17.0 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 25.4, 31.2, 33.6, 56.1, 58.9, 62.0, 115.2, 138.5. IR: 3800-3100, 3075, 2975, 2932, 2859, 1747, 1640, 1458, 1258, 1093, 911 cm^-1.

19

Boc-derivative of epoxy alcohol 2: [α]_D ²⁰ +24.3 (c = 1, CHCl₃), literature data for the enantiomer:¹³ [α]_D ²⁵ -19.9
(c = 1.1, CHCl₃).

21

Diol 5: [α]_D ²⁰ +6.3 (c = 1, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 1.36-1.72 (m, 6 H), 2.02-2.06 (m, 2 H), 3.37 (br s, 2 H, 2 × OH), 3.72-3.87 (m, 3 H), 4.91-5.02 (m, 2 H), 5.78 (ddt, J = 6.6, 10.4, 17.1 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 25.1, 33.9, 37.4, 38.5, 61.7, 72.0, 114.9, 138.9.

22

Silyl ether 6: [α]_D ²⁰ +12.4 (c = 1, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 0.06 (s, 6 H, 2 × Me), 0.88 (s, 9 H, 3 × Me), 1.36-1.64 (m, 6 H), 2.02-2.09 (m, 2 H), 3.75-3.92 (m, 3 H), 4.91-5.02 (m, 2 H), 5.79 (ddt, J = 6.6, 10.4, 17.1 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = -5.35, -5.32, 18.3, 25.0, 26.1 (3 × C), 34.0, 37.2, 38.6, 63.0, 72.0, 114.6, 139.1. IR: 3600-3100, 3075, 2931, 2859, 1642, 1472, 1256, 1090, 1005, 910, 836, 777 cm^-1.

24

Hydroxy ester 7: [α]_D ²⁰ +11.2 (c = 1, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 0.05 (s, 6 H, 2 × Me), 0.86 (s, 9 H, 3 × Me), 1.39-1.64 (m, 6 H), 2.17-2.21 (m, 2 H), 3.45 (br s, 1 H, OH), 3.68 (s, 3 H), 3.69-3.99 (m, 3 H), 5.80 (d, J = 15.6 Hz, 1 H), 6.89-6.99 (m, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ =
-5.3 (2 × C), 18.4, 24.3, 26.1 (3 × C), 32.4, 37.2, 38.5, 51.6, 63.2, 72.2, 121.3, 149.7, 167.4. IR: 3600-3100, 3075, 2931, 2859, 1642, 1472, 1256, 1090, 1005, 910, 836, 777 cm^-1.

26

Compound 8 (trans isomer): [α]_D ²⁰ -43.1 (c = 1, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 0.04 (s, 6 H, 2 × Me), 0.88 (s, 9 H, 3 × Me), 1.24-1.48 (m, 2 H), 1.51-1.70 (m, 5 H), 1.90-2.02 (m, 1 H), 2.41 (dd, J = 5.5, 14.7 Hz, 1 H), 2.59 (dd, J = 8.3, 14.7 Hz, 1 H), 3.60-3.67 (m, 2 H), 3.67 (s, 3 H), 3.89-3.94 (m, 1 H), 4.10-4.16 (m, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = -5.0 (2 × C), 18.6, 18.8, 26.3 (3 × C), 29.9, 30.4, 35.9, 39.9, 51.9, 60.2, 67.9, 69.1, 172.3. IR: 2928, 2856, 1746, 1463, 1361, 1288, 1256, 1206, 1159, 1092, 1050, 836, 776. cis-Isomer: [α]_D ²⁰ -18.2 (c = 1, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 0.03 (s, 6 H, 2 × Me), 0.88 (s, 9 H, 3 × Me), 1.18-1.25 (m, 2 H), 1.46-1.73 (m, 5 H), 1.79-1.84 (m, 1 H), 2.38 (dd, J = 5.8, 14.7 Hz, 1 H), 2.53 (dd, J = 7.5, 14.7 Hz, 1 H), 3.40-3.48 (m, 1 H), 3.66-3.77 (m, 6 H). ¹³C NMR (75 MHz, CDCl₃): δ = -5.0 (2 × C), 18.6, 23.8, 26.3 (3 × C), 31.6, 31.7, 39.9, 42.0, 51.9, 59.9, 74.6, 75.0, 172.3. IR: 2931, 2858, 1746, 1469, 1437, 1255, 1196, 1091, 1047, 836, 776 cm^-1.

27

Compound 9: trans isomer: [α]_D ²⁰ -51.3 (c = 1, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 1.21-1.42 (m, 2 H), 1.51-1.91 (m, 6 H), 2.38 (dd, J = 4.7, 14.4 Hz, 1 H), 2.86 (dd, J = 10.2, 14.4 Hz, 1 H), 3.64-3.77 (m, 5 H), 3.92-3.99 (m, 1 H), 4.28-4.36 (m, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 18.7, 29.5, 30.9, 36.7, 38.3, 52.1, 60.8, 69.0, 70.4, 172.5. IR: 3437, 2940, 2868, 1739, 1439, 1290, 1257, 1206, 1153, 1047, 1021 cm^-1.

31

trans-1: [α]_D ²⁰ -11.3 (c = 0.25, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 1.35-1.39 (m, 2 H), 1.62-1.91 (m, 4 H), 1.90 (dd, J = 1.5, 6.8 Hz, 3 H), 2.44 (dd, J = 5.8, 14.9 Hz, 1 H), 2.62 (dd, J = 6.6, 15.2 Hz, 1 H), 2.66 (dd, J = 8.1, 14.9 Hz, 1 H), 2.88 (dd, J = 6.6, 15.2 Hz, 1 H), 3.66 (s, 3 H), 4.17-4.30 (m, 2 H), 6.13 (dq, J = 1.5, 15.6 Hz, 1 H), 6.85 (dq, J = 6.8, 15.6 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 18.6, 23.5, 31.2, 31.5, 41.9, 47.0, 51.9, 74.8, 75.0, 132.7, 143.6, 172.0, 198.8. IR: 2938, 2860, 1739, 1668, 1626, 1433, 1373, 1352, 1289, 1200, 1066 cm^-1. HRMS (CI): m/z [M + H⁺] calcd for C₁₃H₂₁O₄: 241.1440; found: 241.1436. Chiral HPLC: ChiralPak AD, hexane-i-PrOH (90:10), λ = 225 nm, flow rate: 0.5 mL/min, t _R = 22.4 min (minor) and 25.5 min (major).

32

Compound 9: cis isomer: [α]_D ²⁰ +10.9 (c = 1, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 1.18-1.36 (m, 2 H), 1.46-1.84 (m, 6 H), 2.40 (dd, J = 4.5, 15.0 Hz, 1 H), 2.50 (dd, J = 8.3, 15.0 Hz, 1 H), 3.55-3.62 (m, 1 H), 3.67 (s, 3 H), 3.72-3.82 (m, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 23.5, 31.3, 31.5, 38.2, 41.6, 52.1, 62.0, 74.8, 79.3, 172.2. IR: 3449, 2937, 2857, 1740, 1439, 1375, 1344, 1287, 1251, 1200, 1040 cm^-1.

33

cis-1: [α]_D ²⁰ +10.0 (c = 0.94, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 1.12-1.27 (m, 3 H), 1.49-1.66 (m, 3 H), 1.89 (dd, J = 1.5, 6.9 Hz, 3 H), 2.37 (dd, J = 5.6, 14.9 Hz, 1 H), 2.46-2.53 (m, 2 H), 2.80 (dd, J = 6.8, 15.3 Hz, 1 H), 3.65 (s, 3 H), 3.69-3.86 (m, 2 H), 6.13 (dq, J = 1.5, 15.6 Hz, 1 H), 6.84 (dq, J = 6.9, 15.6 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 18.6, 23.5, 31.2, 31.5, 42.9, 47.0, 51.8, 74.8, 75.0, 132.7, 143.6, 172.0, 198.8. IR: 2937, 2857, 1740, 1668, 1627, 1434, 1375, 1350, 1289, 1198, 1066 cm^-1. HRMS (CI): m/z [M + H⁺] calcd for C₁₃H₂₁O₄: 241.1440; found: 241.1437. Chiral HPLC: ChiralPak AD, hexane-i-PrOH (90:10), λ = 225 nm, flow rate: 0.5 mL/min, t _R = 18.2 min (minor) and 19.9 min (major).

34

After submission of this manuscript, a similar approach was reported in the literature, see: Bates, R. W.; Palani, K. Terahedron Lett. 2008, 49, 2832.