A Facile Total Synthesis of
All Stereoisomers of Tarchonanthuslactone and Euscapholide from
Chiral Epichlorohydrin

Hee-Yoon Lee; Vasu Sampath; Yeokwon Yoon

doi:10.1055/s-0028-1087524

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Synlett 2009(2): 249-252
DOI: 10.1055/s-0028-1087524

LETTER

A Facile Total Synthesis of All Stereoisomers of Tarchonanthuslactone and Euscapholide from Chiral Epichlorohydrin

Hee-Yoon Lee*, Vasu Sampath, Yeokwon Yoon
School of Molecular Science (BK21) and Department of Chemistry, Korea Advanced Institute of Science & Technology (KAIST), Daejon, 305-701, Korea
Fax: +82(42)8698370; e-Mail: leehy@kaist.ac.kr;

Further Information

Publication History

Received 10 October 2008
Publication Date:
15 January 2009 (online)

Abstract
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Abstract

A versatile and facile synthetic route to all the stereoisomers of tarchonanthuslactone and euscapholide was developed using epichlorohydrin as the source of all the chiral centers.

Key words

tarchnanthuslactone - euscapholide - epichlorohydrin - diversity - total synthesis

References and Notes

1 Harris JM. Li M. Scott JG. O’Doherty GA. In Strategies and Tactics in Organic Synthesis Vol. 5: Harmata M. Elsevier; London: 2004. p.221-253

Search in Google Scholar
2 Dakeda JM. Okada Y. Masuda T. Hirata E. Takushi A. Otsuka H. Phytochemistry 1998, 49: 2565

Crossref Search in Google Scholar
3 Dong M. Zhang Q. Hirota M. Tian. Chan. Yau. Yu. Kaifa. 2004, 16: 290; Chem. Abstr. 2004, 143, 33891

Search in Google Scholar
4 Bohlmann F. Suwita A. Phytochemistry 1979, 18: 677

Crossref Search in Google Scholar
5 Hsu FL. Chen YC. Cheng JT. Planta Med. 2000, 66: 228

Thieme Connect Search in Google Scholar
6 Fu X. Sevenet T. Hamid A. Hadi A. Remy F. Pais M. Phytochemistry 1993, 33: 1272

Crossref Search in Google Scholar
7 Murga J. Garcia-Fortanet J. Corda M. Marco JA.
J. Org. Chem. 2004, 69: 7277

Crossref Search in Google Scholar
8 Jodynis-Liebert J. Murias M. Bloszyk E. Planta Med. 2000, 66: 199

Thieme Connect Search in Google Scholar
9 Yadav JS. Kumar NN. Reddy MS. Prasad AR. Tetrahedron 2007, 63: 2689 ; and references therein

Crossref Search in Google Scholar
10a Nakada T. Hata N. Iida K. Oishi T. Tetrahedron Lett. 1987, 46: 5661

Search in Google Scholar
10b Murga J. Garcia-Fortanet J. Corda M. Marco JA. Tetrahedron Lett. 2003, 44: 7909

Search in Google Scholar
11a Umarye JD. Lessmann T. Garcia AB. Mamane V. Sommers S. Waldmann H. Chem. Eur. J. 2007, 13: 3305

Search in Google Scholar
11b Curran DP. Moura-Letts G. Pohlman M. Angew. Chem. Int. Ed. 2006, 45: 2423

Search in Google Scholar
12a Enders D. Steinbusch D. Eur. J. Org. Chem. 2003, 4450
12b Binder JT. Kirsch SF. Chem. Commun. 2007, 4164
13a Ok T. Jeon A. Lim JJ. Hong CS. Lee H.-S.
J. Org. Chem. 2007, 72: 7390

Search in Google Scholar
13b Burova SA. McDonald FE. J. Am. Chem. Soc. 2004, 126: 2495

Search in Google Scholar
13c Gaunt MJ. Hook DE. Tanner HR. Ley SV. Org. Lett. 2003, 5: 4815

Search in Google Scholar
14 Jacobsen E. Acc. Chem. Res. 2000, 33: 421

Crossref PubMed Search in Google Scholar
15 Herb C. Dettner F. Maier ME. Eur. J. Org. Chem. 2005, 728

Crossref
16 Yamaguchi M. Hirao I. Tetrahedron Lett. 1983, 24: 391

Crossref Search in Google Scholar
18 Constantino MG. Carvalho I. Jose da Silva GV. Archanjo FC. Molecules 1996, 1: 72

Crossref Search in Google Scholar
19 Barbazanges M. Meyer C. Cossy J. Org. Lett. 2007, 9: 3245

Crossref PubMed Search in Google Scholar
20 Müller T. Margraf D. Syha Y. J. Am. Chem. Soc. 2005, 127: 10852

Crossref PubMed Search in Google Scholar
21 Aggarwal VK. Bae I. Lee H.-Y. Tetrahedron 2004, 60: 9725

Crossref Search in Google Scholar
22 Garaas SD. Hunter TJ. O’Doherty GA. J. Org. Chem. 2002, 67: 2682

Crossref Search in Google Scholar
23 Takeda Y. Okada Y. Masuda T. Hirata E. Shinzato T. Takushi A. Yu Q. Otsuka H. Chem. Pharm. Bull. 2000, 48: 752

Crossref Search in Google Scholar

17

All new compounds showed satisfactory analytical data for the assigned structure and purity. Spectroscopic Data for Selected Compounds
Compound 1d: [α]_D +142.8 (c 0.55, CHCl₃), lit. [²] [α]^³0 +115.5 (c 1.52, MeOH). ^¹H NMR (400 MHz, CDCl₃): δ = 6.88-6.84 (dt, J = 10.1, 3.4 Hz, 1 H), 6.01-5.98 (dt, J = 9.8, 1.8 Hz, 1 H), 4.65-4.58 (m, 1 H), 4.09-4.04 (m, 1 H), 2.40-2.37 (m, 2 H), 2.02-1.95 (m, 1 H), 1.77-1.72 (dt, J = 12.6, 4.1 Hz, 1 H), 1.23 (d, J = 6.3 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 163.9, 145.1, 121.2, 76.8, 65.2, 43.6, 29.5, 23.7.
Compound 1a: [α]_D -115.5 (c 0.17, CHCl₃), lit. [²²] [α]^²5 -111 (c 1, CHCl₃). ^¹H NMR (400 MHz, CDCl₃): δ = 6.89-6.84 (ddd, J = 13.9, 6.7, 4.6 Hz, 1 H), 6.01-5.97 (dt, J = 9.7, 1.7 Hz, 1 H), 4.65-4.58 (m, 1 H), 4.08-4.03 (m, 2 H), 2.40-2.36 (m, 2 H), 2.07 (br, 1 H), 2.02-1.95 (m, 1 H), 1.76-1.71 (dt, J = 12.6, 4.2 Hz, 1 H), 1.23 (d, J = 6.2 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 164.0, 145.2, 121.2, 76.8, 65.2, 43.5, 29.4, 23.7.
Compound 4a: [α]_D -76.2 (c 0.22, CHCl₃), [α]^²5 -76
(c 0.6, CHCl₃). ^¹H NMR (400 MHz, CDCl₃): δ = 6.81-6.78 (ddd, J = 10.0, 5.0, 2.4 Hz, 1 H), 6.73-6.70 (m, 2 H), 6.59-6.56 (dd, J = 8.1, 2.0 Hz, 1 H), 5.99-5.96 (ddd, J = 10.0, 3.0, 1.0 Hz, 1 H), 5.05-5.01 (m, 1 H), 4.16 (m, 1 H), 2.81 (t, J = 6.5 Hz, 2 H), 2.58 (t, J = 7.2 Hz, 2 H), 2.29 (m, 1 H), 2.20 (m, 1 H), 2.04-2.01 (m, 1 H), 1.76-1.70 (m, 1 H), 1.23 (d, J = 6.3 Hz, 3 H), 0.95 (s, 9 H), 0.94 (s, 9 H), 0.15 (s, 6 H), 0.14 (s, 6 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 172.7, 165.0, 145.4, 143.9, 142.2, 132.8, 120.9, 120.4, 115.4, 115.2, 75.2, 67.0, 41.0, 35.8, 30.1, 29.0, 20.5.
Compound 4b: [α]_D -9.5 (c 0.2, CHCl₃). ^¹H NMR (400 MHz, CDCl₃): δ = 6.85-6.81 (m, 1 H), 6.72 (d, J = 8.1 Hz,
1 H), 6.66 (d, J = 2.0 Hz, 1 H), 6.57-6.55 (dd, J = 8.1, 2.1 Hz, 1 H), 6.01-5.97 (ddd, J = 11.6, 5.8, 1.9 Hz, 1 H), 5.13-5.09 (m, 1 H), 4.22-4.18 (m, 1 H), 2.84-2.77 (m, 2 H), 2.55 (t, J = 6.9 Hz, 2 H), 2.26-2.22 (m, 2 H), 1.89-1.86 (dd, J = 9.4, 3.2 Hz, 1 H), 1.81-1.77 (dd, J = 9.7, 3.2 Hz, 1 H), 1.22 (d, J = 6.3 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 172.4, 164.8, 145.3, 143.6, 142.6, 132.6, 121.1, 120.4, 115.29, 74.3, 66.9, 41.2, 36.2, 30.3, 29.5, 20.4.
Compound 4c: [α]_D +9.7 (c 0.3, CHCl₃). ^¹H NMR (300 MHz, CDCl₃): δ = 6.85-6.82 (m, 1 H), 6.74-6.65 (m, 2 H), 6.58-6.54 (dd, J = 8.0, 2.0 Hz, 1 H), 6.01-5.97 (ddd, J = 11.6, 5.8, 1.8 Hz, 1 H), 5.15-5.08 (m, 1 H), 4.21-4.18 (m,
1 H), 2.82-2.77 (m, 2 H), 2.55 (t, J = 6.8 Hz, 2 H), 2.25-2.21 (m, 2 H), 1.89-1.85 (dd, J = 9.3, 3.3 Hz, 1 H), 1.81-1.77 (dd, J = 9.5, 3.4 Hz, 1 H), 1.22 (d, J = 6.3 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 172.5, 164.9, 145.4, 143.6, 142.5, 132.6, 121.0, 120.4, 115.2, 74.4, 66.9, 41.2, 36.1, 30.3, 29.5, 20.4.
Compound 4d: [α]_D +91.5 (c 0.5, CHCl₃). ^¹H NMR (400 MHz, CDCl₃): δ = 6.82-6.79 (ddd, J = 10.3, 5.4, 2.5 Hz,
1 H), 6.73-6.70 (m, 2 H), 6.58-6.55 (dd, J = 8.0, 2.0 Hz, 1 H), 5.99-5.96 (m, 1 H), 5.05-5.01 (m, 1 H), 4.16 (m, 1 H), 2.81 (m, 2 H), 2.58 (t, J = 7.2 Hz, 2 H), 2.28 (m, 1 H), 2.20 (m, 1 H), 2.04-2.01 (m, 1 H), 1.76-1.71 (m, 1 H), 1.23 (d, J = 6.43 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 172.7, 165.0, 145.5, 143.9, 142.2, 132.8, 120.9, 120.3, 115.4, 75.2, 67.1, 40.9, 35.8, 30.1, 28.9, 20.4. Compound 12: ^¹H NMR (400 MHz, C₆D₆-CDCl₃, 1:1): δ = 4.36-4.34 (m, 1 H), 3.84 (m, 1 H), 3.63-3.58 (m, 1 H), 2.55-2.51 (br d, J = 19.0 Hz, 1 H), 2.30-2.23 (dd, J = 19.1, 5.4 Hz, 1 H), 1.64-1.60 (br d, J = 13.9 Hz, 1 H), 1.46-1.42 (m, 1 H), 1.31 (m, 1 H), 1.10-1.03 (m, 1 H), 0.91 (d, J = 6.0 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 169.4, 72.9, 65.9, 61.9, 38.6, 36.5, 29.4, 21.4.