Synthesis of α,β-Unsaturated Pseudogeminal [2.2]Paracyclophane Bisketones

Abstract

An unexpected synthesis of α,β-unsaturated pseudo­geminal [2.2]paracyclophane bisketones has been realized via a ­dyotropic-type rearrangement of the corresponding bisallenyl o-nitrophenyl sulfoxides.

[2.2]paracyclophanes - sulfoxides - allenes - rearrangement

References and Notes

1 Greiving H. Hopf H. Jones PG. Bubenitschek P. Desvergne J.-P. Bouas-Laurent H. Eur. J. Org. Chem.  2005,  558 

2 Hopf H. Greiving H. Beck C. Dix I. Jones PG. Desvergne J.-P. Bouas-Laurent H. Eur. J. Org. Chem.  2005,  567 

3 For a review, see: Hopf H. Angew. Chem. Int. Ed.  2003,  42:  2822 ; Angew. Chem. 2003, 115, 2928

4 Birsa ML. Jones PG. Braverman S. Hopf H. Synlett  2005,  640 

5 Braverman S. In The Chemistry of Sulfenic Acids and their Derivatives   Patai S. Wiley; New York: 1990.  p.311 

6 Braverman S. In The Chemistry of Double-Bonded Functional Groups, Supplement A2   Patai S. Wiley; Chichester: 1989.  p.963 

7

Compound 3a (0.35 g, 50%); mp 118-119 °C. IR (neat): 2927, 1960, 1515, 1337, 1063, 733 cm^-1. ¹H NMR (200 MHz, CDCl₃, TMS): δ = 1.05 (t, ³ J = 7 Hz, 6 H, 2 × Me), 1.62 (sext., ³ J = 7 Hz, 4 H, 2 × CH₂), 2.47 (dt, ³ J = 7, ⁵ J = 3 Hz, 4 H, 2 × CH₂), 2.95 (m, 6 H, 3 × CH₂), 3.05 (m, 1 H, CH₂), 3.42 (m, 1 H, CH₂), 6.38 (m, 6 H, 6 × CH_Ar), 6.58 (t, ⁵ J = 3 Hz, 2 H, 2 × CH_allene), 7.40 (m, 2 H, 2 × CH_Ar), 7.65 (m, 2 H, 2 × CH_Ar), 7.88 (m, 2 H, 2 × CH_Ar), 8.35 (m, 2 H, 2 × CH_Ar) (selected NMR data for one isomer). ¹³C NMR (50 MHz, CDCl₃, TMS): δ = 13.9 (q), 21.5 (t), 30.1 (t), 32.3 (t), 34.7 (t), 101.6 (d), 115.9 (s), 124.1 (d), 125.2 (d), 126.4 (d), 131.0 (d), 132.9 (d), 133.2 (d), 133.5 (d), 135.2 (s), 137.8 (s), 140.0 (s), 142.1 (s), 144.3 (s), 204.6 (s) (selected NMR data for one isomer). MS-ESI: m/z = 729 [M⁺ + 23]. Anal. Calcd for C₄₀H₃₈N₂O₆S₂: C, 67.97; H, 5.42; N, 3.96; S, 9.07. Found: C, 67.79; H, 5.24; N, 3.77; S, 9.17.

8

Compound 4a (0.17 g, 85%); viscous oil. IR (neat): 2960, 1683, 1655, 1584, 1366, 1183, 728 cm^-1. ¹H NMR (200 MHz, CDCl₃, TMS): δ = 0.97 (t, ³ J = 7 Hz, 6 H, 2 × Me), 1.62 (sext, ³ J = 7 Hz, 4 H, 2 × CH₂), 2.54 (t, ³ J = 7 Hz, 4 H, 2 × CH₂), 3.05 (m, 6 H, 3 × CH₂), 3.09 (m, 1 H, CH₂), 3.61 (m, 1 H, CH₂), 6.37 (d, ³ J = 16 Hz, 2 H, 2 × CH), 6.56 (m, 4 H, 4 × CH_Ar), 6.74 (m, 2 H, 2 × CH_Ar), 7.60 (d, ³ J = 16 Hz, 2 H, 2 × CH). ¹³C NMR (50 MHz, CDCl₃, TMS): δ = 13.7 (q), 17.5 (t), 32.6 (t), 34.8 (t), 42.5 (t), 126.4 (d), 130.2 (d), 134.7 (s), 134.8 (d), 135.1 (d), 139.4 (d), 139.9 (s), 140.0 (s), 200.1 (s). MS-EI: m/z (%) = 400 (20) [M⁺], 383 (15), 329 (25), 187 (21), 129 (100). Anal. Calcd for C₂₈H₃₂O₂: C, 83.96; H, 7.99. Found: C, 83.64; H, 7.70.

9

Compound 7 (0.25 g, 85%); viscous oil. IR (neat): 2954, 1974, 1534, 1342, 1052, 729 cm^-1. ¹H NMR (200 MHz, CDCl₃, TMS): δ = 2.05 (t, ⁵ J = 3.3 Hz, 3 H, Me), 6.15 (t, ⁵ J = 3.3 Hz, 1 H, CH_allene), 7.00 (m, 2 H, 2 × CH_Ar), 7.15 (m, 3 H, 3 × CH_Ar), 7.31 (m, 1 H, CH_Ar), 7.52 (m, 1 H, 2 × CH_Ar), 7.75 (m, 1 H, CH_Ar), 8.22 (m, 1 H, CH_Ar) (selected NMR data for one isomer). ¹³C NMR (50 MHz, CDCl₃, TMS): δ = 13.0 (q), 100.4 (d), 112.5 (s), 125.0 (s), 126.3 (d), 126.9 (d), 127.0 (d), 127.1 (d), 127.3 (d), 128.1 (d), 128.6 (d), 128.7 (d), 131.3 (s), 134.5 (d), 134.8 (s), 203.6 (s) (selected NMR data for one isomer). MS (ESI): m/z = 322 [M⁺ + 23]. Anal. Calcd for C₁₆H₁₃NO₃S: C, 64.20; H, 4.38; N, 4.68; S, 10.71. Found: C, 63.94; H, 4.19; N, 4.54; S, 10.48.

10 Baliah V. Ekambaram A. J. Indian Chem. Soc.  1991,  68:  272 

For reviews see:

11a Minkin VI. Olekhnovich LP. Zhdanov YA. Molecular Design of Tautomeric Compounds   D. Reidel Publishing Co.; Dordrecht: 1988.  p.221 

11b Reetz MT. Adv. Organomet. Chem.  1977,  16:  33 

12 Mackenzie K. Proctor G. Woodnutt DJ. Tetrahedron  1987,  43:  5981 ; and references cited therein