Synthesis of γ-Alkylidene α,β-Unsaturated δ-Lactones by Ring-Closing Metathesis: Application to the Synthesis of the C1-C8 Subunit of Biselide E

Abstract

The synthesis of γ-alkylidene α,β-unsaturated δ-lactones was achieved by ring-closing metathesis of acrylates derived from (1,3-butadien-2-yl)methanols. The application to the synthesis of the C1-C8 subunit of biselide E is reported.

ring-closing metathesis - 1,3-dienes - lactones - cross-coupling reactions - biselide E

References and Notes

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12

Propargyl acrylate did not react with olefin 11 by ene-yne cross-metathesis [Grubbs II (5-10 mol%), CH₂Cl₂, reflux, 4-8 h; trace of lactones 10a,c detected by TLC] and did also not produce the γ-methylene α,β-unaturated lactone 12 by ene-yne RCM (vide infra).

13 For a review on macrocyclizations by RCM (including 1,3-dienes as olefinic partners), see: Gradillas A. Pérez-Castells J. Angew. Chem. Int. Ed.  2006,  45:  6086 

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19

( E )-5-[( tert -Butyldiphenylsilyloxy)propylidene]-5,6-dihydropyran-2-one (10a) IR: 1721, 1427, 1391, 1248, 1221, 1199, 1091, 1027, 820, 786, 733, 700, 613 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 7.64-7.62 (m, 4 H), 7.46-7.36 (m, 6 H), 7.21 (dd, J = 9.9, 1.1 Hz, 1 H), 5.90 (dd, J = 9.9, 1.8 Hz, 1 H), 5.76 (m, 1 H), 4.83 (m, app. br d, J = 1.2 Hz, 2 H), 3.74 (t, J = 6.3 Hz, 2 H), 2.46-2.41 (m, 2 H), 1.04 (s, 9 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 164.1 (s), 139.0 (d), 135.5 (d, 4 C), 133.4 (s, 3 C), 131.7 (d), 129.8 (d, 2 C), 127.7 (d, 4 C), 119.0 (d), 71.1 (t), 62.5 (t), 31.0 (t), 26.8 (q, 3 C), 19.1 (s). MS (EI, 70 eV): m/z (%) = 377 (1) [M - Me⁺], 355 (64) [M - t-Bu⁺], 307 (9), 306 (27), 305 (100), 257 (19), 227 (17), 200 (15), 199 (80), 197 (16), 183 (13), 181 (18), 167 (7), 135 (18), 105(10), 91 (6), 77 (12). HRMS-FAB: m/z calcd for C₂₄H₂₈NaO₃Si [M + Na⁺]: 415.1699; found: 415.1692.

20 Alonso DA. Najera C. Sansano JM. Tetrahedron  1994,  50:  6603 ; compound 12 is sensitive and can undergo polymerization upon concentration of its solutions

21

( Z )-5-[( tert -Butyldiphenylsilyloxy)propylidene]-5,6-dihydropyran-2-one (10c) IR: 1719, 1644, 1427, 1221, 1104, 937, 820, 738, 700, 613 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 7.65-7.62 (m, 4 H), 7.46-7.37 (m, 6 H), 6.92 (d, J = 9.7 Hz, 1 H), 5.85-5.81 (m, 2 H), 5.00 (m, app. br s, 2 H), 3.75 (t, J = 6.2 Hz, 2 H), 2.33 (dt, app. q, J = 6.4 Hz, 2 H), 1.04 (s, 9 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 163.7 (s), 145.0 (d), 135.5 (d, 4 C), 133.8 (d), 133.3 (s, 2 C), 129.8 (d, 2 C), 128.7 (s), 127.7 (d, 4 C), 116.7 (d), 66.6 (t), 62.3 (t), 31.6 (t), 26.8 (q, 3 C), 19.1 (s). HRMS-FAB: m/z calcd for C₂₄H₂₈NaO₃Si [M + Na⁺]: 415.1699; found: 415.1693.

22

For a similar observation in the cross-metathesis between 1,2-substituted-1,3-butadienes and 1-alkenes, see ref. 14a.

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28

The geometric isomers (Z/E = 95:5) were easily separated by flash chromatography.

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30

( E )-3-(4,4-Dichlorobut-3-enylidene)-6-methoxy-3,6-dihydro-2 H -pyran (22)
IR: 1684, 1619, 1446, 1384, 1300, 1187, 1158, 1103, 956, 872, 749 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 6.61 (d, J = 10.2 Hz, 1 H), 5.95-5.83 (m, 1 H), 5.82 (t, J = 7.4 Hz, 1 H), 5.29 (t, J = 7.8 Hz, 1 H), 4.91 (d, J = 2.8 Hz, 1 H), 4.49 (d, AB syst, J = 13.0 Hz, 1 H), 3.99 (d, AB syst, J = 13.0 Hz, 1 H), 3.45 (s, 3 H), 3.02 (app. td, J = 7.6, 1.2 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 130.9 (s), 127.0 (d), 126.6 (d), 123.7 (d), 121.7 (d), 121.3 (s), 95.5 (d), 62.6 (t), 55.4 (q), 27.2 (t). HRMS-FAB: m/z calcd for C₁₀H₁₂ ^³5Cl₂NaO₂ [M + Na⁺]: 257.01066; found: 257.01065.