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

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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.