A New Way to Generate Functionalized
Bridges in [2,2]Cyclophanes

M. Lucian Birsa; Henning Hopf

doi:10.1055/s-0029-1218286

LETTER

A New Way to Generate Functionalized Bridges in [2,2]Cyclophanes

M. Lucian Birsa*^a,b, Henning Hopf^a
^a Institute of Organic Chemistry, Technical University Braunschweig, Hagenring 30, 38106 Braunschweig, Germany
^b Department of Organic Chemistry, ‘Al. I. Cuza’ University of Iasi, 11 Carol I, 700506 Iasi, Romania
Fax: +40(232)201313; e-Mail: lbirsa@uaic.ro;

Abstract

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Abstract

The synthesis of valuable precursors of cyclic endiynes has been accomplished by base-catalyzed intramolecular cyclization of pinacolone-type compounds.

Key words

[2,2]paracyclophanes - hydrogen transfer -

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Referenzen

References and Notes

1 Brown CJ. Farthing AC. Nature (London) 1949, 164: 915

2 Cram DJ. Steinberg H. J. Am. Chem. Soc. 1951, 73: 5691

3 Vögtle F. Neumann P. Synthesis 1973, 85

4 Staab HA. Knaus GH. Henke H.-E. Krieger C. Chem. Ber. 1983, 116: 2785

5 Boekelheide V. Top. Curr. Chem. 1983, 113: 87

6 Hopf H. Marquard C. In Strain and its Implications in Organic Chemistry de Meijere A. Blechert S. Eds . Kluwer; Dordrech: 1983. p.297

7 Hopf H. Psiorz M. Chem. Ber. 1986, 119: 1836

8 Werner C. Hopf H. Grunenberg J. Ernst L. Jones PG. Köhler F. Herges R. Eur. J. Org. Chem. 2009, 2621

For reviews, see:

9a Hopf H. Angew. Chem. Int. Ed. 2003, 42: 2822 ; Angew. Chem. 2003, 115, 2928

9b Hopf H. Bondarenko L. Ernst L. Jones PG. Grunenberg J. Hentschel S. Dix I. Greiving H. Chem. Eur. J. 2007, 13: 3950

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

11 Birsa ML. Hopf H. Synlett 2007, 2753

12 Brown CJ. J. Chem. Soc. 1953, 3278

13 Nicolau KC. Zuccarello G. Ogawa Y. Schweiger EJ. Kumazawa T. J. Am. Chem. Soc. 1988, 110: 4866

14 Gleiter R. Ritter J. Angew. Chem. Int. Ed. 1994, 33: 2470 ; Angew. Chem. 1994, 106, 2550

15 Haberhauer G. Gleiter R. J. Am. Chem. Soc. 1999, 121: 4664

16 Birsa ML. Jones PG. Hopf H. Eur. J. Org. Chem. 2005, 3263

17

Compound 1a: Yield: 1.2 g (83%); mp 210-211 ˚C. IR (ATR): 3240, 2922, 2223, 1482, 1261, 1005, 719 cm^-¹. ^¹H NMR (200 MHz, CDCl₃, TMS): δ = 1.71 (d, ⁵ J = 3.4 Hz, 6 H, 2 × Me), 3.02 (m, 2 H, CH₂), 3.09 (s, 4 H, 2 × CH₂), 3.45 (m, 2 H, CH₂), 4.05 (br s, 2 H, 2 × OH), 5.65 (q, ⁵ J = 3.4 Hz, 2 H, 2 × CH), 6.52 (m, 4 H, 4 × CH_Ar), 6.81 (m, 2 H, 2 × CH_Ar). ^¹³C NMR (50 MHz, CDCl₃, TMS): δ = 3.7 (q), 31.4 (t), 35.1 (t), 61.5 (d), 79.2 (s), 82.1 (s), 127.4 (d), 132.9 (d), 134.6 (s), 135.1 (d), 139.4 (s), 140.1 (s). MS (EI): m/z (%) = 326 (22)[M⁺ - H₂O], 171 (15), 155 (100), 141 (38), 128 (35), 115 (30). Anal. Calcd for C₂₄H₂₄O₂: C, 83.69; H, 7.02. Found: C, 83.76; H, 6.95.

18

Compound 3b: Yield: 0.26 g (42%); mp 228-229 ˚C. IR (ATR): 2925, 1665, 1480, 1314, 1229, 1005, 767, 698 cm^-¹. ^¹H NMR (400 MHz, CD₂Cl₂, TMS): δ = 2.75 (m, 1 H, CH₂), 2.95 (m, 1 H, CH₂), 2.98-3.30 (m, 4 H, 2 × CH₂), 3.40 (m, 1 H, CH₂), 3.95 (m, 1 H, CH₂), 3.47 and 5.09 (ABq, ^² J = 14.7 Hz, 2 H, CH ₂CO), 6.46 (d, ^³ J = 7.7 Hz, 1 H, CH_Ar), 6.55 (d, ⁴ J = 2.0 Hz, 1 H, CH_Ar), 6.64 (d, ^³ J = 7.9 Hz, 1 H, CH_Ar), 6.65 (dd, ^³ J = 7.7 Hz, ⁴ J = 1.9 Hz, 1 H, CH_Ar), 6.80 (dd, ^³ J = 7.9 Hz, ⁴ J = 2.0 Hz, 1 H, CH_Ar), 7.06 (d, ⁴ J = 1.9 Hz, 1 H, CH_Ar), 7.15-7.34 (m, 10 H, 10 × CH_Ar). ^¹³C NMR (100 MHz, CD₂Cl₂, TMS): δ = 32.4 (t), 34.0 (t), 34.9 (t), 35.2 (t), 48.7 (t), 99.4 (s), 101.0 (s), 122.2 (s), 126.2 (s), 127.5 (d), 127.6 (d), 128.2 (d, 2 C), 128.6 (d, 2 C), 129.3 (d, 2 C), 129.9 (d, 2 C), 131.1 (d), 132.9 (d), 133.4 (d), 135.2 (d), 137.0 (s), 138.0 (d), 138.3 (d), 139.1 (s), 139.5 (s), 139.9 (s), 140.1 (s), 142.4 (s), 142.5 (s), 150.6 (s), 201.5 (s). MS (EI): m/z (%) = 450 (100)[M⁺], 317 (32), 303 (35), 233 (98), 217 (95), 191 (18), 131 (28). Anal. Calcd for C₃₄H₂₆O: C, 90.63; H, 5.82. Found: C, 90.79; H, 5.75.

19 Hopf H. Wachholz G. Chem. Ber. 1987, 120: 1259

20 Mallory FB. Mallory CW. Org. React. 1984, 30: 1

21 Hopf H. Mlynek C. El-Tamany S. Ernst L. J. Am. Chem. Soc. 1985, 107: 6620

22 Hopf H. Mlynek C. J. Org. Chem. 1990, 55: 1361

23

Compound 4: Yield: 0.1 g (23%); mp 142-143 ˚C. IR (ATR): 2927, 1663, 1485, 1434, 762, 730 cm^-¹. ^¹H NMR (400 MHz, CDCl₃, TMS): δ = 2.77-3.15 (m, 4 H, 2 × CH₂), 3.32 (m, 2 H, CH₂), 3.55 (m, 1 H, CH₂), 3.93 (m, 1 H, CH₂), 4.57 and 5.26 (ABq, ^² J = 15.6 Hz, 2 H, CH ₂CO), 6.48 (d, ^³ J = 8.0 Hz, 1 H, CH_Ar), 6.65 (d, ⁴ J = 2.0 Hz, 1 H, CH_Ar), 6.68 (dd, ^³ J = 8.2 Hz, ⁴ J = 1.9 Hz, 1 H, CH_Ar), 6.70 (d, ^³ J = 8.2 Hz, 1 H, CH_Ar), 6.83 (dd, ^³ J = 8.0 Hz, ⁴ J = 2.0 Hz,
1 H, CH_Ar), 7.26 (d, ⁴ J = 1.9 Hz, 1 H, CH_Ar), 7.7 (m, 4 H, 4 × CH_Ar), 8.22 (dd, ^³ J = 7.6 Hz, ⁴ J = 2.0 Hz, 1 H, CH_Ar), 8.39 (dd, ^³ J = 7.6 Hz, ⁴ J = 1.9 Hz, 1 H, CH_Ar), 8.72 (dd, ^³ J = 8.0 Hz, ⁴ J = 1.9 Hz, 1 H, CH_Ar), 8.78 (dd, ^³ J = 8.0 Hz, ⁴ J = 2.0 Hz, 1 H, CH_Ar). ^¹³C NMR (100 MHz, CD₂Cl₂, TMS): δ = 32.5 (t), 33.74 (t), 33.75 (t), 35.1 (t), 40.5 (t), 97.6 (s), 103.4 (s), 119.7 (s), 122.6 (d), 123.3 (d), 125.1 (d), 126.0 (s), 126.9 (d), 127.1 (d), 127.2 (d), 127.3 (d, 2 C), 129.5 (s), 130.1 (s), 130.6 (s), 131.1 (d), 132.0 (s), 132.9 (d), 133.1 (d), 135.0 (d), 137.8 (d), 137.9 (d), 138.9 (s), 139.0 (s), 139.4 (s), 140.2 (s), 142.1 (s), 142.4 (s), 200.9 (s). MS (EI): m/z (%) = 448 (100)[M⁺], 405 (24), 315 (43), 302 (25), 131 (18). Anal. Calcd for C₃₄H₂₄O: C, 91.04; H, 5.39. Found: C, 91.22; H, 5.27.