Hetero-Diels-Alder Reaction of 3-Bromo-7-(bromomethyl)tetracyclo[5.3.1.02,6.04,8]undec-10(12)-ene-9,11-dione with Pentafulvenes: Facile Synthesis of Novel Polycyclic Cage Compounds Having a Pyran Ring

Beena James; E. Suresh; Mangalam S. Nair

doi:10.1055/s-2006-956481

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Synlett 2006(20): 3479-3483
DOI: 10.1055/s-2006-956481

LETTER

Hetero-Diels-Alder Reaction of 3-Bromo-7-(bromomethyl)tetracyclo[5.3.1.0^2,6.0^4,8]undec-10(12)-ene-9,11-dione with Pentafulvenes: Facile Synthesis of Novel Polycyclic Cage Compounds Having a Pyran Ring

Beena James^a, E. Suresh^b, Mangalam S. Nair*^a
^a Organic Chemistry Section, Regional Research Laboratory (CSIR), Trivandrum 695019, India
Fax: +91(471)2491712; e-Mail: msn555in@yahoo.co.in;
^b Analytical Science Discipline, Central Salt and Marine Chemicals Research Institute (CSIR), Bhavnagar 364002, India

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Publication History

Received 24 June 2006
Publication Date:
08 December 2006 (online)

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Abstract

The enone moiety of 3-bromo-7-(bromomethyl)tetracyclo[5.3.1.0^2,6.0^4,8]undec-10(12)-ene-9,11-dione undergoes facile hetero-Diels-Alder reaction with pentafulvenes leading to novel cage systems with pyran moiety

Key words

polycyclic cage system - hetero-Diels-Alder reaction - pentafulvenes - pyran moiety

References and Notes

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15

Crystal Data for Compound 6a: C₂₇H₂₄Br₂O₂, colorless plates, 0.20 × 0.10 × 0.05 mm³; formula weight = 540.28; monoclinic, space group: P2₁/c; unit cell dimensions: a = 12.4363(16) Å, b = 14.1854(18) Å, c = 12.8075(16) Å, β = 91.000(2)°; V = 2259.1 (5) Å³; Z = 4; D(calcd) = 1.589 Mg/m³; F(000) = 1088; absorption coefficient = 3.610 mm^-1; GoF = 0.992; R indices(I >2σ): R1 = 0.0565, wR2 = 0.1345. Crystal structure data for 6a have been deposited at the Cambridge Crystallographic Data Centre and the allocated deposition number is CCDC 602750.

16

Spectroscopic Data for Selected Compounds. Data for 6a: crystallized from CH₂Cl₂-hexane (1:5) mixture; mp 135-137 °C. Yield: 65%. FT-IR (KBr): 2974, 1751, 1665, 1243, 1228, 1176, 1070, 893, 692 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.22-7.46 (m, 5 H), 6.83-6.93 (m, 1 H), 6.57 (d, J = 15.3 Hz, 1 H), 6.26 (d, J = 5.7 Hz, 1 H), 6.15 (d, J = 11.4 Hz, 1 H), 6.02 (d, J = 5.4 Hz, 1 H), 5.29 (d, J = 5.7 Hz, 1 H), 4.29 (s, 1 H), 3.61 (d, J = 10.2 Hz, 1 H), 3.37-3.44 (q, J = 15.3 Hz, 1 H), 3.29 (d, J = 10.2 Hz, 1 H), 2.99-3.04 (t, J ₁ = 6.3 Hz, J ₂ = 7.5 Hz, 1 H), 2.84 (d, J = 4.5 Hz, 1 H), 2.63-2.74 (m, 3 H), 2.38-2.49 (m, 2 H), 2.02-2.10 (m, 1 H), 1.85 (d, J = 11.1 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 203.2, 149.8, 148.8, 137.5, 135.5, 132.7, 129.7, 128.9, 128.7, 127.6, 126.3, 125.2, 121.5, 103.5, 81.8, 55.5, 55.4, 54.1, 49.9, 45.8, 45.6, 45.0, 36.7, 35.4, 31.6, 28.2, 22.6. HRMS (EI): m/z [M⁺] calcd for C₂₇H₂₄O₂Br₂: 538.0143; found: 538.0132.
Data for 6b: crystallized from CH₂Cl₂-hexane (1:5) mixture; mp 124-126 °C. Yield: 61%. FT-IR (KBr): 2969, 1746, 1670, 1233, 1008, 974, 677, 653 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.46 (s, 1 H), 6.43 (s, 1 H), 6.25-6.27 (t, J ₁ = 3.3 Hz, J ₂ = 2.4 Hz, 2 H), 6.12 (s, 1 H), 5.99 (d, J = 3.6 Hz, 1 H), 5.30 (d, J = 6.9 Hz, 1 H), 4.29 (s, 1 H), 3.67-3.74 (dd, J = 6.9 Hz, 1 H), 3.62 (d, J = 10.2 Hz, 1 H), 3.27 (d, J = 10.2 Hz, 1 H), 2.98-3.02 (t, J ₁ = 6.6 Hz, J ₂ = 6.0 Hz, 1 H), 2.82 (d, J = 4.5 Hz, 1 H), 2.61-2.70 (m, 3 H), 2.56 (d, J = 8.4 Hz, 1 H), 2.34 (d, J = 4.5 Hz, 1 H), 1.93-2.01 (dd, J ₁ = J ₂ = 6.6 Hz, 1 H), 1.84 (d, J = 11.4 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 203.2, 152.6, 148.3, 146.9, 142.1, 137.2, 135.9, 111.6, 109.5, 109.1, 82.3, 55.6, 53.9, 49.9, 45.9, 45.6, 45.0, 37.9, 35.4, 31.6, 27.4, 22.6, 14.I. HRMS: m/z [M⁺] calcd for C₂₃H₂₀O₃Br₂: 501.9779; found: 501.9768.
Data for 6f: crystallized from CH₂Cl₂-hexane (1:5) mixture; mp 146-148 °C. Yield: 64%. FT-IR (KBr): 3434, 1756, 1665, 1226, 1243, 869, 658 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 8.62 (d, J = 4.5 Hz, 1 H), 7.63-7.58 (t, J ₁ = 6.0 Hz, J ₂ = 7.5 Hz, 1 H), 7.15 (d, J = 7.8 Hz, 1 H) 7.05-7.09 (t, J ₁ = 4.8 Hz, J ₂ = 7.2 Hz, 1 H), 6.30-6.35 (m, 2 H), 6.15 (d, J = 5.4 Hz, 1 H), 5.30 (d, J = 6.3 Hz, 1 H), 4.32 (s, 1 H), 4.20-4.28 (m, 1 H), 3.62 (d, J = 10.5 Hz, 1 H), 3.28 (d, J = 10.2 Hz, 1 H), 2.97-3.01 (t, J ₁ = 7.2 Hz, J ₂ = 6.3 Hz, 1 H), 2.82 (d, J = 4.5 Hz, 1 H), 2.61-2.76 (m, 4 H), 2.34 (d, J = 5.1 Hz, 1 H), 1.82-1.93 (m, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 203.3, 156.0, 153.7, 149.4, 148.0, 139.3, 136.6, 136.1, 124.3, 120.5, 120.1, 104.5, 82.4, 55.7, 55.4, 53.9, 49.9, 46.3, 45.9, 45.0, 37.9, 35.4, 31.6, 27.8. HRMS: m/z [M⁺] calcd for C₂₄H₂₁NO₂Br₂: 512.9939; found: 512.9943.
Data for 6g: crystallized from CH₂Cl₂-hexane (1:5) mixture; mp 154-156 °C. Yield: 54%. FT-IR (KBr): 2983, 1737, 1670, 1636, 1230, 740, 668 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 8.21 (s, 1 H), 7.63 (s, 1 H), 7.38 (d, J = 8.4 Hz, 1 H) 7.21-7.26 (m, 2 H), 6.57 (s, 1 H), 6.48 (s, 1 H), 6.34 (d, J = 5.7 Hz, 1 H), 5.95 (d, J = 5.4 Hz, 1 H), 5.34 (d, J = 6.9 Hz, 1 H), 4.23 (s, 1 H), 3.72-3.79 (m, 1 H), 3.61 (d, J = 10.2 Hz, 1 H), 3.27 (d, J = 10.2 Hz, 1 H), 2.92-2.96 (d, J ₁ = 6.9 Hz, J ₂ = 6.6 Hz, 1 H), 2.79 (d, J = 4.5 Hz, 1 H), 2.59-2.65 (m, 3 H), 2.42-2.51 (m, 1 H), 2.33 (s, 1 H), 1.99-2.01 (m, 1 H), 1.82 (d, J = 11.4 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 207.4, 148.5, 146.5, 138.3, 137.1, 134.3, 133.9, 124.6, 123.3, 123.0, 122.2, 120.5, 111.1, 104.9, 102.9, 82.9, 55.6, 53.9, 49.9, 45.9, 45.6, 44.9, 37.3, 35.4, 29.7, 26.5, 24.7. HRMS: m/z [M⁺] calcd for C₂₇H₂₃NO₂Br₂: 551.0096; found: 551.0087.