Multiple Stille Cross-Coupling Reactions with Tribenzotriquinacenes and Fenestrindanes - En Route to Extended Convex/Concave and Saddle-Shaped Carbon Frameworks

Abstract

Hexabromotribenzotriquinacenes and octabromotetrabenzo[5.5.5.5]fenestranes undergo highly efficient multiple Stille cross-coupling reactions, yielding building blocks for extended convex/concave and saddle-shaped molecular scaffolds, respectively.

triquinacenes - fenestranes - fenestrindanes - Stille cross-coupling - multiple C-C coupling

References

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The crystallographic data for 3 have been deposited at CCDC under the registry number 271522. They can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: [phone]; e-mail: [e-mail]]. The unit cell parameters and the X-ray diffraction intensities were recorded on a Nonius Kappa CCD area detector. The structure was solved by the direct method (SHELXS). Empirical formula: C₂₆H₁₈Br₆ + 2 C₄H₈O. Formula weight: 954.07. T = 100 (2) K. Wavelength: 0.71073 Å. Crystal system: monoclinic, P2₁/c. Unit cell dimensions: a = 13.1750 (17) Å, b = 7.4460 (8) Å, c = 34.504 (4) Å, β = 96.721 (11)°; V = 3361.6 (7) ų; Z = 4, ρ_caldc = 1.885 g/cm³. Absorption coefficient: 7.196 mm^-1, F(000): 1856. Crystal size: 0.30 ¥ 0.11 ¥ 0.05 mm³. Theta range for data collection: 3.11-27.50°. Index ranges: -17 ≤ h ≤ 17, -9 ≤ k ≤ 9, -43 ≤ l ≤ 44. Reflections collected/unique: 45553/7718 [R(int) = 0.0589]. Completeness to Θ = 27.50, 99.9%. Absorption correction multi-scan: Max. and min. transmission 1.000000 and 0.475662. Refinement method: Full-matrix least-squares on F². Data/restraints/parameters: 7718/0/383. Goodness-of-fit on F²: 1.048. Final R indices [I>2σ(I)] R1 = 0.0340, wR2 = 0.0623 [6043]. R indices (all data) R1 = 0.0546, wR2 = 0.0678. Largest diff. peak and hole: 1.049 and -0.656 e Å^-3. Remark: largest diff. peak near Br(6) (1.27 Å).

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Cyranski, M.; Kuck, D. unpublished results.

<A NAME="RW00105ST-24">24</A>

Compound 6: ¹H NMR (300 MHz, CDCl₃): δ = 1.32 (s, 3 H), 1.62 (s, 9 H), 3.31 (d, J = 6.3 Hz, 12 H, CH₂), 5.01 (dd, J = 18.6, 1.5 Hz, 6 H, =CH₂), 5.03 (dd, J = 9.6, 1.5 Hz, 6 H, =CH₂), 5.84-5.89 (m, 6 H, CH=), 7.10 (s, 6 H, ArH). ¹³C NMR (75 MHz, CDCl₃): δ = 16.07 (p), 25.81 (p), 37.16 (s), 62.24 (q), 70.33 (q), 115.74 (s), 123.48 (t), 137.18 (q), 137.18 (t), 147.14 (q). HRMS (ESI): m/z calcd for C₄₄H₅₂N [M + NH₄]⁺: 594.4094; found: 594.4092.

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<A NAME="RW00105ST-28">28</A>

General Experimental Procedure.
An oven-dried flask equipped with a magnetic stirring bar was charged under argon with the aryl bromide (0.05 mmol) in THF (20 mL, 40 mL for compound 4). Then, Pd(PPh₃)₄ (6 mg, 0.005 mmol) and CsF (0.72 mmol for 3, 0.96 mmol for 4) were added, and then the organotin reagent (0.36 mmol for 3, 0.48 mmol for 4) was added via a syringe. The flask was evacuated and refilled with argon five times. The mixture was stirred at 45 °C for about 10 h (16 h for the preparation of compound 7) and quenched with H₂O. After vigorous shaking, the mixture was filtered and the aqueous layer was extracted with EtOAc. The combined organic layers were washed with brine, dried over Na₂SO₄, concentrated, and purified by column chromatography.

<A NAME="RW00105ST-29">29</A>

Compound 7: ¹H NMR (300 MHz, CDCl₃): δ = 1.27 (s, 3 H), 1.60 (s, 9 H), 5.16 (dd, J = 11.4, 1.8 Hz, 6 H, =CH₂), 5.41 (dd, J = 17.0, 1.8 Hz, 6 H, =CH₂), 6.81 (dd, J = 17.0, 11.4 Hz, 6 H, CH=), 7.23 (s, 6 H, ArH). ¹³C NMR (75 MHz, CDCl₃): δ = 16.08 (p), 25.79 (p), 62.41 (q), 70.90 (q), 115.87 (s), 120.65 (t), 135.33 (t), 136.27 (q), 148.61 (q). HRMS (ESI): m/z calcd for C₃₈H₃₇ [M + H]⁺: 493.2890; found: 493.2899.

<A NAME="RW00105ST-30">30</A>

Compound 8: ¹H NMR (400 MHz, CDCl₃): δ = 1.39 (s, 3 H), 1.74 (s, 9 H), 5.90 (d, J = 3.2 Hz, 6 H), 6.38-6.40 (m, 6 H), 7.43 (dd, J = 3.2, 0.8 Hz, 6 H), 7.63 (s, 6 H, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 16.05 (p), 25.74 (p), 62.61 (q), 70.99 (q), 107.97 (t), 111.30 (t), 123.56 (t), 129.30 (q), 141.58 (t), 148.53 (q), 153.06 (q). HRMS (ESI): m/z calcd for C₅₀H₄₀O₆N [M + NH₄]⁺: 750.2850; found: 750.2840.

<A NAME="RW00105ST-31">31</A>

Compound 9: ¹H NMR (400 MHz, CDCl₃): δ = 1.46 (s, 3 H), 1.78 (s, 9 H), 6.79 (dd, J = 3.6, 1.2 Hz, 6 H), 6.92 (dd, J = 4.8, 3.6 Hz, 6 H), 7.22 (dd, J = 4.8, 0.8 Hz, 6 H), 7.50 (s, 6 H, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 16.17 (p), 25.75 (p), 62.62 (q), 71.07 (q), 125.56 (t), 125.77 (t), 126.78 (t), 127.02 (t), 134.07 (q), 142.83 (q), 148.40 (q). HRMS (DEI): m/z calcd for C₅₀H₃₆S₆ [M⁺]: 828.1141; found: 828.1133.

<A NAME="RW00105ST-32">32</A>

Compound 10: ¹H NMR (300 MHz, CDCl₃): δ = 1.23 (s, 12 H), 3.36 (d, J = 6.0 Hz, 8 H, CH₂), 3.46 (d, J = 5.7 Hz, 8 H, CH₂), 4.98 (d, J = 17.1 Hz, 8 H, =CH₂), 5.06 (d, J = 10.8 Hz, 8 H, =CH₂), 5.90-6.07 (m, 8 H, CH=), 6.95 (s, 4 H, ArH), 7.22 (s, 4 H, ArH). ¹³C NMR (75 MHz, CDCl₃): δ = 28.48 (p), 37.19 (s), 37.34 (s), 58.61 (q), 89.21 (q), 115.51 (s), 122.53 (t), 124.65 (t), 136.50 (q), 136.94 (q), 137.43 (t), 137.60 (t), 145.29 (q), 150.20 (q). HRMS (ESI): m/z calcd for C₅₇H₆₄N [M + NH₄]⁺: 762.5033; found: 762.5022.

<A NAME="RW00105ST-33">33</A>

Compound 12: ¹H NMR (400 MHz, CDCl₃): δ = 1.47 (s, 12 H), 6.00 (d, J = 3.6 Hz, 4 H), 6.08 (d, J = 3.2 Hz, 4 H), 6.42-6.45 (m, 8 H), 7.45 (d, J = 1.2 Hz, 4 H), 7.47 (s, 4 H), 7.48-7.49 (m, 4 H), 7.82 (s, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 28.17 (p), 58.96 (q), 89.19 (q), 108.19 (t), 111.38 (t), 111.53 (t), 122.63 (t), 124.09 (t), 129.03 (q), 141.68 (q), 141.68 (t), 146.45 (q), 151.28 (q), 153.10 (q). HRMS (ESI): m/z calcd for C₆₅H₄₅O₈ [M + H]⁺: 953.3109; found: 953.3116.

<A NAME="RW00105ST-34">34</A>

Compound 13: ¹H NMR (400 MHz, CDCl₃): δ = 1.52 (s, 12 H), 6.92 (dd, J = 3.6, 1.2 Hz, 4 H), 6.94-6.97 (m, 12 H), 7.26 (dd, J = 6.4, 1.2 Hz, 8 H), 7.37 (s, 4 H), 7.63 (s, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 28.58 (p), 59.01 (q), 89.38 (q), 124.32 (t), 125.90 (t), 126.22 (t), 126.86 (t), 127.20 (t), 133.47 (q), 133.69 (q), 142.94 (q), 143.07 (q), 146.28 (q), 151.17 (q). Various attempts to characterize 13 by mass spectrometry, including DEI, APCI and MALDI as ionization techniques, were unsuccessful.

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