Vinylogous Nicholas Reactions
in the Synthesis of Icetexane, Faveline, and Related Ring
Systems

Izabela Kolodziej; James R. Green

doi:10.1055/s-0030-1261221

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Synlett 2011(16): 2397-2401
DOI: 10.1055/s-0030-1261221

LETTER

Vinylogous Nicholas Reactions in the Synthesis of Icetexane, Faveline, and Related Ring Systems

Izabela Kolodziej, James R. Green*
Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, N9B 3P4, Canada
Fax: +1(519)9737098; e-Mail: jgreen@uwindsor.ca;

Further Information

Publication History

Received 11 July 2011
Publication Date:
08 September 2011 (online)

Abstract
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Abstract

The intramolecular vinylogous Nicholas reactions of aryl substituted acetoxy enyne-Co₂(CO)₆ complexes afford tricyclic 6,7,6-ring systems and related systems in good yield.

Key words

carbocations - alkyne complexes - electrophilic aromatic substitution - cyclization - fused ring systems

References and Notes

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21

Analytical Data for Selected Compounds
Compound 4g: IR (KBr): ν_max = 2954, 2833, 2187, 1673 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 10.35 (s, 1 H), 6.96 (d, J = 3.1 Hz, 1 H), 6.90 (dd, J = 9.1, 3.1 Hz, 1 H), 6.83 (d, J = 9.1 Hz, 1 H), 3.86 (s, 3 H), 3.79 (s, 3 H), 2.73 (m, 2 H), 2.55 (m, 2 H), 1.83 (m, 2 H), 1.70 (m, 1 H), 1.48 (m, 1 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 193.0, 154.9, 153.2, 148.2, 145.9, 117.5, 116.8, 112.0, 111.9, 96.7, 91.9, 56.4, 55.8, 37.4, 32.3, 25.7, 24.2. MS: m/e = 284 [M⁺]. HRMS: m/e calcd for C₁₈H₂₀O₃ [M⁺] 284.1412; found: 284.1412. Compound 5g: IR (KBr): ν_max = 2964, 1746 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 6.93 (d, J = 2.9 Hz, 1 H), 6.81 (d of 0.5 ABquart, J = 2.9, 8.9 Hz, 1 H), 6.78 (0.5 ABquart, J = 8.9 Hz, 1 H), 4.97 (s, 2 H), 3.84 (s, 3 H), 3.77 (s, 3 H), 2.51 (m, 2 H), 2.32 (m, 2 H), 2.09 (s, 3 H), 1.79 (m, 2 H), 1.62 (m, 2 H), 1.53 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 171.2, 154.4, 153.1, 145.1, 126.0, 117.4, 115.4, 113.3, 111.9, 94.9, 89.9, 68.0, 56.4, 55.8, 34.6, 32.3, 31.2, 26.1, 26.0, 21.0. MS: m/e = 328 [M⁺]. HRMS: m/e calcd for C₂₀H₂₄O₄ [M⁺]: 328.1675; found: 328.1683.
Compound 1g: IR (KBr): ν_max = 2926, 2085, 2058, 2013, 1741 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.01 (d, J = 3.1 Hz, 1 H), 6.86 (dd, J = 8.9, 3.1 Hz, 1 H), 6.75 (d, J = 8.9 Hz, 1 H), 4.53 (s, 2 H), 3.81 (s, 3 H), 3.75 (s, 3 H), 2.61 (m, 2 H), 2.31 (m, 2 H), 1.95 (s, 3 H), 1.83 (m, 2 H), 1.55-1.64 (m, 4 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 199.8, 170.9, 153.5, 150.1, 139.1, 138.6, 127.7, 117.2, 113.5, 110.2, 95.8, 91.0, 65.6, 58.7, 54.4, 37.5, 32.6, 32.3, 26.6, 26.3, 20.8. MS: m/e = 558 [M⁺ - 2CO], 530 [M⁺ - 3CO], 446 [M⁺ - 5CO]. HRMS: m/e calcd for C₂₆H₂₄Co₂O₁₀ [M - 2CO⁺]: 558.0106; found: 558.0117.

22

Compound 8a: IR (KBr): ν_max = 2930, 2087, 2046, 2017 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.20 (d, J = 2.7 Hz, 1 H), 7.04 (d, J = 8.4 Hz, 1 H), 6.84 (dd, J = 8.4, 2.7 Hz, 1 H), 3.85 (s, 3 H), 3.20 (s, 2 H), 2.33-2.38 (m, 2 H), 2.26-2.30 (m, 2 H), 1.73-1.78 (m, 2 H), 1.66-1.72 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 200.0, 159.0, 139.1, 137.2, 130.1, 129.9, 129.3, 117.4, 113.6, 94.9, 89.5, 55.3, 42.1, 33.7, 30.5, 23.0, 22.7. MS: m/e = 510 [M⁺], 482 [M⁺ - CO], 454 [M⁺ - 2CO], 426 [M⁺ - 3CO], 398 [M⁺ - 4CO]. HRMS: m/e calcd for C₂₂H₁₆Co₂O₇ [M - CO⁺]: 481.9611; found: 481.9634.
Compound 8a′: IR (KBr): ν_max = 2933, 2087, 2046, 2017 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.28 (dd, obscured, 1 H), 7.23 (apparent t, J = 7.8 Hz, 1 H), 6.90 (dd, J = 8.0, 1.1 Hz, 1 H), 3.86 (s, 3 H), 3.33 (s, 2 H), 2.30-2.38 (m, 4 H), 1.73-1.79 (m, 2 H), 1.65-1.71 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 200.1, 155.8, 139.5, 137.5, 130.8, 127.5, 125.3, 124.7, 110.5, 95.1, 89.9, 55.9, 33.7, 32.2, 30.4, 23.0, 22.7. MS: m/e = 510 [M⁺], 482 [M⁺ - CO], 454 [M⁺ - 2CO], 426 [M⁺ - 3CO], 398 [M⁺ - 4CO]. HRMS: m/e calcd for C₂₂H₁₆Co₂O₇ [M⁺ - CO]: 481.9611; found: 481.9624.
Compound 8b: IR (KBr): ν_max = 2964, 2085, 2046, 2026 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 6.92 (d, J = 8.9 Hz, 1 H), 6.75 (d, J = 8.9 Hz, 1 H), 3.87 (s, 3 H), 3.82 (s, 3 H), 3.34 (s, 2 H), 2.29-2.37 (m, 4 H), 1.73-1.79 (m, 2 H), 1.65-1.72 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 200.5, 153.9, 150.2, 136.2, 131.4, 127.3, 126.5, 112.0, 108.6, 95.9, 84.7, 56.6, 54.7, 33.5, 32.7, 30.5, 23.0, 22.6. MS: m/e = 512 [M⁺ - CO], 484 [M⁺ - 2CO], 428 [M⁺ - 4CO]. HRMS: m/e calcd for C₂₃H₁₈Co₂O₈: 539.9666; found: 539.9669.
Compound 8c: IR (KBr): ν_max = 2935, 2085, 2043, 2012 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.13 (s, 1 H), 6.64 (s, 1 H), 3.92 (s, 6 H), 3.19 (s, 2 H), 2.34-2.39 (m, 2 H), 2.26-2.31 (m, 2 H), 1.74-1.79 (m, 2 H), 1.68-1.73 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 200.1, 149.2, 148.4, 136.3, 130.4, 129.7, 114.6, 112.3, 95.1, 90.5, 56.0, 42.6, 33.8, 30.5, 23.0, 22.7. HRMS: m/e calcd for C₂₃H₁₈Co₂O₈ [M⁺ - CO]: 511.9716; found: 511.9711.
Compound 8d: IR (KBr): ν_max = 2936, 2085, 2045, 2016 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 6.98 (s, 1 H), 3.92 (s, 3 H), 3.89 (s, 3 H), 3.88 (s, 3 H), 3.25 (s, 2 H), 2.36 (m, 2 H), 2.31 (m, 2 H), 1.77 (m, 2 H), 1.70 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 200.1, 152.4, 150.4, 142.8, 137.0, 133.7, 130.8, 123.3, 111.0, 95.2, 90.3, 61.6, 60.8, 56.0, 33.7, 32.8, 30.4, 23.0, 22.7. MS: m/e = 458 [M⁺ - 4CO], 430 [M⁺ - 5CO], 402 [M⁺ - 6CO]. HRMS: m/e calcd for C₂₄H₂₀Co₂O₉ [M⁺ - CO]: 541.9822; found: 541.9821.
Compound 8e: IR (KBr): ν_max = 2931, 2084, 2049, 2015, 1638 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.14 (apparent t, J = 7.7 Hz, 2 H), 7.09 (s, 1 H), 7.06 (t, J = 6.9 Hz, 1 H), 6.89 (d, J = 8.2 Hz, 2 H), 5.32 (s, 1 H), 3.98 (s, 3 H), 3.92 (s, 3 H), 3.86 (s, 3 H), 2.63-2.72 (m, 1 H), 2.50-2.60 (m, 1 H), 2.27-2.48 (m, 2 H), 1.82-1.95 (m, 2 H), 1.68-1.77 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 199.7, 152.7, 151.6, 142.8, 141.0, 138.3, 132.7, 131.4, 128.4, 126.8, 126.3, 125.0, 112.2, 91.6, 61.7, 60.8, 55.7, 47.6, 35.8, 31.4, 23.4, 22.8. MS: m/e = 562 [M⁺ - 3CO], 534 [M⁺ - 4CO], 478 [M⁺ - 6CO]. HRMS: m/e calcd for C₃₀H₂₄Co₂O₉ [M⁺ - 3CO]: 562.0237; found: 562.0240.
Compound 8f: IR (KBr): ν_max = 2938, 2087, 2048, 2019 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 6.99 (s, 1 H), 3.91 (s, 3 H), 3.89 (s, 3 H), 3.85 (s, 3 H), 3.48 (s, 2 H), 2.71 (m, 2 H), 2.56 (m, 2 H), 2.06 (apparent quin, J = 7.5 Hz, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 199.7, 152.3, 150.8, 142.9, 141.5, 135.2, 133.4, 121.5, 112.2, 90.9, 87.9, 61.2, 60.8, 55.9, 39.2, 35.4, 27.4, 22.5. MS: m/e = 472 [M⁺ - 3CO], 444 [M⁺ - 4CO], 416 [M⁺ - 5CO], 388 [M⁺ - 6CO]. HRMS: m/e calcd for C₂₃H₁₈Co₂O₉ [M⁺ - CO]: 527.9654; found: 527.9666.
Compound 8g: IR (KBr): ν_max = 2937, 2085, 2051, 2029 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 6.92 (d, J = 8.9 Hz, 1 H), 6.74 (d, J = 8.9 Hz, 1 H), 3.86 (s, 3 H), 3.81 (s, 3 H), 3.40 (s, 2 H), 2.76 (m, 1 H), 2.51-2.57 (m, 4 H), 2.29 (m, 1 H), 1.75-1.81 (m, 2 H), 1.61-1.72 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 200.0, 153.8, 150.1, 141.6, 136.7, 130.9, 126.7, 112.2, 108.5, 97.6, 56.8, 54.6, 38.5, 35.5, 34.6, 31.4, 29.7, 26.2. MS: m/e = 526 [M⁺ - CO], 498 [M⁺ - 2CO], 442 [M⁺ - 4CO]. HRMS: m/e calcd for C₂₄H₂₀Co₂O₈ [M⁺]: 553.9822; found: 553.9802.
Compound 8h: IR (KBr): ν_max = 2918, 2085, 2046, 2016cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 6.97 (s, 1 H), 3.92 (s, 3 H), 3.89 (s, 3 H), 3.87 (s, 3 H), 3.31 (s, 2 H), 2.56 (m, 4 H), 1.79 (m, 2 H), 1.65 (m, 2 H), 1.59 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 200.1, 152.4, 150.3, 142.89, 142.85, 136.3, 133.5, 123.3, 110.7, 97.1, 90.9, 61.7, 60.9, 56.0, 39.0, 35.4, 34.9, 31.6, 26.24, 26.19. MS: m/e = 584 [M⁺], 556 [M⁺ - CO], 528 [M⁺ - 2CO], 500 [M⁺ - 3CO], 472 [M⁺ - 4CO], 444 [M⁺ - 5CO], 414 [M⁺ - 6CO]. HRMS: m/e calcd for C₂₅H₂₂Co₂O₉ [M⁺ - 2CO]: 528.0029; found: 528.0030.
Compound 10: IR (KBr): ν_max = 3035, 2919, 1607, 1516 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 6.66 (s, 1 H), 6.65 (s, 1 H), 6.64 (s, 1 H), 6.60 (s, 1 H), 3.861 (s, 3 H), 3.860 (s, 6 H), 3.85 (s, 3 H), 2.86 (apparent t, J = 13.1 Hz, 1 H), 2.76 (dd, J = 14.2, 10.6 Hz, 1 H), 2.62-2.75 (m, 3 H), 2.61 (dd, J = 14.2, 6.9 Hz, 1H), 2.32 (d, J = 14.2 Hz, 1 H), 1.97 (m, 1 H), 1.89 (m, 1 H), 1.80 (m, 1 H), 0.95-1.75 (m, 22 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 146.51, 146.45, 146.44, 146.3, 135.4, 135.1, 134.3, 113.8, 113.1, 112.5, 112.4, 56.00, 55.95, 55.90, 48.5, 43.9, 43.7, 38.0, 36.3, 35.8, 35.4, 34.9, 26.7, 26.4. MS: m/e = 260 [M⁺]. HRMS: m/e calcd for C₁₇H₂₄O₂: 260.1776; found: 260.1775.

23

Typical Experimental Procedure
To a solution of 1f (0.406 g, mmol) in CH₂Cl₂ (9 mL) at 0 ˚C was added BF₃˙OEt₂ (25 µL, 0.20 mmol). After stirring for 45 min, aq NH₄Cl was added and the mixture subjected to a conventional extractive workup (CH₂Cl₂). Flash chromatography (PE-Et₂O = 1:1) afforded 8f (0.0319 g, 87% yield) as a viscous red-brown oil.