γ-Allenyl Allyl Benzothiazole Sulfonyl Anions Undergo cis-Selective (Sylvestre) Julia Olefinations

Abstract

γ-Allenyl allyl benzothiazolyl sulfones 8 and ent-8 provided allenyl trienes and polyenes with cis-selectivities ranging from 71:29 to 100:0 upon condensation (NaHMDS, THF, -78 °C to 25 ºC) with a variety of unsaturated aldehydes.

Julia olefination - stereoselectivity - allenes - polyenes

References

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Synthesis of non-commercial aldehydes 12:

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<A NAME="RG39104ST-24D">24d</A>

See for 12g: This vinylogous epoxy-retinal butenolide was acquired by inversion of the steps leading to the ring-deoxygenated peridinin skeleton (see ref. 11): Vaz, B.; Alvarez, R.; de Lera, A. R., manuscript in preparation.

Scheme 4

Scheme 5

<A NAME="RG39104ST-25">25</A>

Data for 13f: ¹H NMR (600 MHz, CDCl₃): δ = 9.45 (s, 1 H, CHO), 6.98 (dd, J = 14.4, 11.8 Hz, 1 H, H₁₅), 6.95 (d, J = 11.9 Hz, 1 H, H_{14 ′}), 6.68 (dd, J = 14.4, 11.7 Hz, 1 H, H_{15 ′}), 6.59 (d, J = 12.1 Hz, 1 H, H₁₀), 6.38 (t, J = 12.0 Hz, 1 H, H₁₁), 6.33 (d, J = 12.1 Hz, 1 H, H₁₄), 6.11 (s, 1 H, H₈), 5.95 (d, J = 11.9 Hz, 1 H, H₁₂), 2.13 (s, 3 H, C₁₃-CH3), 1.90-1.80 (m, 1 H, H₃), 1.87 (s, 3 H, C_{13 ′}-CH₃), 1.85 (s, 3 H, C₉-CH₃), 1.80-1.70 (m, 1 H, H₂ or H₄), 1.60-1.50 (m, 3 H, H₂ + H₃ + H₄), 1.40-1.30 (m, 1 H, H₂ or H₄), 1.32 (s, 3 H, C₅-CH₃), 1.27 (s, 3 H, C₁-CH₃), 1.04 (s, 3 H, C₁-CH₃) ppm. MS (EI⁺): m/z (%) = 367 (27) [M⁺ + 1], 366 (100) [M⁺], 322 (35), 281 (41), 202 (28), 157 (36), 111 (37), 109 (32), 99 (27), 97 (60), 95 (27), 85 (61), 83 (62), 81 (30), 71 (80), 69 (85). HRMS (EI⁺): m/z calcd for C₂₅H₃₄O₂: 366.2559; found: 366.2555. FT-IR (NaCl): ν = 3600-3400 (br, OH), 2960 (s, C-H), 2923 (s, C-H), 2853 (m, C-H), 1930 (w, C=C=C), 1731 (s, C=O), 1662 (s), 1552 (m), 1261 (s) cm^-1. UV (MeOH): λ_max = 294, 416 nm (Figure [1] ).

Figure 1

<A NAME="RG39104ST-26">26</A>

Data for 13g: ¹H NMR [600 MHz, (CD₃)₂CO]: δ = 7.50 (s, 1 H, H₁₀), 7.17 (d, J = 15.6 Hz, 1 H, H₇), 7.10 (t, J = 12.8 Hz, 1 H, H_{15 ′}), 6.76 (t, J = 12.3 Hz, 1 H, H₁₅), 6.70-6.60 (m, 2 H, H_{10 ′} + H₁₄), 6.47 (t, J = 10.4 Hz, 1 H, H_{11 ′}), 6.42 (d, J = 15.6 Hz, 1 H, H₈), 6.22 (t, J = 11.5 Hz, 1 H, H_{14 ′}), 6.18 (s, 1 H, H_{8 ′}), 6.00 (s, 1 H, H₁₂), 3.54 (s, 1 H, OH), 2.21 (d, J = 6.0 Hz, 3 H, C₁₃-CH₃), 2.00 (m, 1 H, H_{3 ′}), 1.89 (s, 3 H, C_{9 ′}-CH₃), 1.90-1.80 (m, 2 H, H_{4 ′} + H₄), 1.60-1.50 (m, 1 H, H_{2 ′}), 1.50-1.30 (m, 7 H, H_{3 ′} + H_{2 ′} + H_{4 ′} + H₂ + 2 H₃ + H₄), 1.36 (s, 3 H, C_{1 ′}-CH₃), 1.28 (s, 3 H, C_{5 ′}-CH₃), 1.16 (s, 3 H, C₁-CH₃), 1.13 (s, 3 H, C₅-CH₃), 1.10-1.00 (m, 1 H, H₂), 1.01 (s, 3 H, C_{1 ′}-CH₃), 0.91 (s, 3 H, C₁-CH₃) ppm. ¹³C NMR [100 MHz, (CD₃)₂CO]: δ = 204.4 (s, C_{7 ′}), 170.2 (s, C=O), 149.1 (s, C₁₁), 139.8 (d, C₁₄), 138.7 (d, C₁₀), 137.9 (s, C_{9 ′}), 135.7 (s, C₁₃), 135.3 (d, C₇), 134.1 (d, C_{15 ′}), 131.5 (d, C₁₅), 130.4 (d, C_{12 ′}), 129.6 (d, C_{11 ′}), 126.5 (s, C₉), 124.4 (d, C_{10 ′}), 123.6 (d, C₈), 121.3 (s, C_{6 ′}), 120.5 (d, C₁₂), 104.4 (d, C_{8 ′}), 72.7 (s, C₆), 71.7 (s, C_{5 ′}), 67.3 (s, C₅), 42.6 (t, C_{4 ′}), 42.4 (t, C_{2 ′}), 37.5 (t, C₂), 36.2 (s, C_{1 ′}), 35.3 (s, C₁), 33.6 (q, C_{1 ′}-CH₃), 32.6 (q, C_{5 ′}-CH₃), 31.7 (t, C₄), 30.2 (q, C_{1 ′}-CH₃), 27.4 (q, C₁-CH₃), 27.1 (q, C₁-CH₃), 22.0 (q, C₅-CH₃), 20.0 (t, C_{3 ′}), 18.7 (t, C₃), 16.5 (q, C₁₃-CH₃), 15.2 (q, C_{9 ′}-CH₃) ppm. MS (FAB⁺): m/z (%) = 558 (10) [M⁺ + 2], 557 (11) [M⁺ + 1], 556 (85) [M⁺], 540 (12), 539 (26), 394 (15), 393 (26), 322 (27), 307 (29), 289 (20), 241 (12), 165 (27). HRMS (FAB⁺): m/z calcd for C₃₇H₄₉O₄: 557.3631; found: 557.3613. FT-IR (NaCl): ν = 3600-3400 (br, OH), 2961 (s, C-H), 2923 (s, C-H), 2849 (m, C-H), 1926 (w, C=C=C), 1749 (s, C=O), 1521 (w), 1449 (w) cm^-1 (Figure [2] ).

Figure 2

<A NAME="RG39104ST-27">27</A>

Determined by 2D HMQC-TOCSY. Although the geometry of 1,ω-bis(tributylstannyl)-1,3,5,7,9-decapentaene (16) reported by our group was in error (ref.⁹), the structures of the final carotenoids β,β-carotene and (3R,3′R)-zeaxanthin obtained by Stille coupling of 16 with the corresponding trienyliodides are correct. Isomerization takes place at the carotenoid stage by the action of palladium, since reagent 16 is stable to the Stille coupling reaction conditions.

<A NAME="RG39104ST-28">28</A> Smith AB. Wan Z. J. Org. Chem.  2000,  65:  3738