The Hiratani-Double-Claisen Rearrangement as a Key Step in the Preparation of Sequential Bis(8-hydroxyquinoline) Ligands

Abstract

Symmetric and sequential isobutenylidene-bridged bis-(8-hydroxyquinoline)s are prepared by application of the Hiratani-double-Claisen rearrangement as a key step in the reaction sequence. The formation of a dinuclear helicate-type zinc(II) complex is also described.

8-hydroxyquinoline - complexes - Claisen rearrangement - self-assembly - supramolecular chemistry

References and Notes

1 Hollingshead RGW. Oxine and its Derivatives   Butterworth; London: 1954. 

2a Pohl R. Montes VA. Shinar J. Anzenbacher P. J. Org. Chem.  2004,  69:  1723 

2b VanDeun R. Fias P. Nockemann P. Schepers A. Parac-Vogt T. VanHecke K. VanMeervelt L. Binnemans K. Inorg. Chem.  2004,  43:  8461 

2c Imbert D. Comby S. Chauvin A.-S. Bünzli J.-CG. Chem. Commun.  2005,  1432 

3a Albrecht M. Blau O. Synthesis  1997,  213 

For reviews on helicates, see:

3b Piguet C. Bernardinelli G. Hopfgartner G. Chem. Rev.  1997,  97:  2005 

3c Albrecht M. Chem. Rev.  2001,  101:  3457 

3d Hannon MJ. Childs LJ. Supramol. Chem.  2004,  16:  7 

4 Hiratani K. Takahashi T. Kasuga K. Sugihara H. Fujiwara K. Ohashi K. Tetrahedron Lett.  1995,  36:  5567 

5 Albrecht M. Blau O. Wegelius E. Rissanen K. New J. Chem.  1999,  667 

6 Albrecht M. Blau O. Fröhlich R. Proc. Natl. Acad. Sci. U.S.A.  2002,  99:  4876 

7 Piguet C. Hopfgartner G. Bocquet B. Schaad O. Williams AF. J. Am. Chem. Soc.  1994,  116:  9092 

8 Shrader WD. Celebuski J. Kline SI. Johnson D. Tetrahedron Lett.  1988,  29:  1351 

9

Characterization of 5: ¹H NMR (300 MHz, CDCl₃): δ = 8.22 (d, J = 8.2 Hz, 2 H), 7.69 (t, J = 8.2 Hz, 2 H), 7.67 (d, J = 8.2 Hz, 2 H), 7.44 (d, J = 8.2 Hz, 2 H), 7.40 (br d, J = 7.7 Hz, 2 H), 5.59 (s, 2 H), 5.09 (s, 4 H). MS (EI): m/z = 392 [M + H]⁺. Characterization of 6: ¹H NMR (300 MHz, CDCl₃): δ = 8.28 (d, J = 8.4 Hz, 1 H), 7.62 (t, J = 8.2 Hz, 1 H), 7.48 (d, J = 8.2 Hz, 1 H), 7.40 (d, J = 8.4 Hz, 1 H), 7.23 (br d, J = 7.4 Hz, 1 H), 5.49 (s, 1 H), 5.48 (s, 1 H), 4.97 (s, 2 H), 4.33 (s, 2 H). MS (EI): m/z = 223 [M + H]⁺. Characterization of 7: ¹H NMR (300 MHz, CDCl₃): δ = 10.07 (s, 2 H), 8.50 (d, J = 8.5 Hz, 2 H), 7.92 (d, J = 8.2 Hz, 2 H), 7.51 (d, J = 8.2 Hz, 2 H), 7.44 (d, J = 8.5 Hz, 2 H), 4.66 (s, 2 H), 3.53 (s, 4 H). Characterization of 8: ¹H NMR (300 MHz, DMSO-d ₆): δ = 8.39 (d, J = 8.7 Hz, 2 H), 8.14 (d, J = 8.4 Hz, 2 H), 7.51 (d, J = 8.24, 2 H), 7.44 (d, J = 8.5 Hz, 2 H), 4.66 (s, 2 H), 3.53 (s, 4 H). MS (EI): m/z = 427.3 [M + H]⁺.

10

Characterization of 9: ¹H NMR (300 MHz, CDCl₃): δ = 8.92 (dd, J = 8.4, 1.8 Hz, 1 H), 8.22 (d, J = 8.5 Hz, 1 H), 8.12 (dd, J = 8.2, 1.8 Hz, 1 H), 7.69 (d, J = 8.3 Hz, 1 H), 7.40 (m, 7 H), 5.58 (s, 2 H), 5.11 (s, 2 H), 5.05 (s, 2 H). Characterization of 10: ¹H NMR (300 MHz, CDCl₃): δ = 8.75 (dd, J = 4.4, 1.6 Hz, 1 H), 8.24 (d, J = 8.3 Hz, 1 H), 8.10 (dd, J = 8.2, 1.4 Hz, 1 H), 7.94 (br s, 1 H), 7.65 (d, J = 8.6 Hz, 1 H), 7.57 (d, J = 8.6 Hz, 1 H), 7.30 (m, 4 H), 4.91 (s, 1 H), 4.86 (s, 1 H), 3.67 (s, 2 H), 3.65 (s, 2 H). Characterization of 11-H₃: Mp 136 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 8.81 (dd, J = 4.2, 1.7 Hz, 1 H), 8.48 (d, J = 8.4 Hz, 1 H), 8.27 (dd, J = 8.4, 1.5 Hz, 1 H), 8.08 (d, J = 8.2 Hz, 1 H), 7.48 (m, 3 H), 7.35 (s, 2 H), 4.70 (s, 2 H), 3.58 (s, 2 H), 3.55 (s, 2 H). MS (ESI+): m/z = 387 [M + H]⁺. Anal. Calcd for C₂₃H₁₈O₄N₂·0.66H₂O: C, 69.34; H, 4.89; N, 7.03. Found: C, 69.21; H, 4.76; N, 6.92.

11

Characterization of K₂[(11)₂Zn₂]: ¹H NMR (300 MHz, DMSO-d ₆): δ = 8.45 (d, J = 8.2 Hz, 1 H), 8.34 (m, 1 H), 7.96 (m, 2 H), 7.53 (d, J = 8.2 Hz, 1 H), 7.36 (m, 2 H), 6.92 (m, 2 H), 4.81 (s, 1 H). 4.18 (s, 1 H); the signals of the benzylic protons are hidden under the solvent and water peaks. MS (ESI+): m/z = 899 [M + H]⁺. Anal. Calcd for C₄₆H₃₀O₈N₄Zn₂K₂·5H₂O: C, 51.84; H, 3.78; N, 5.26. Found: C, 51.82; H, 3.37; N, 4.95.

12a

Rb₂[(11)₂Zn₂]: ¹H NMR (300 MHz, DMSO-d ₆): δ = 8.31 (m, 3 H), 7.92 (d, J = 8.2 Hz, 1 H), 7.54 (dd, J = 8.2, 4.7 Hz, 1 H), 7.35 (m, 2 H), 6.85 (m, 2 H), 4.43 (m, 2 H). 3.78 (d, J = 15.3 Hz, 1 H), 3.36 (d, J = 8.7 Hz, 1 H); two further signals are hidden under the water peak.

12b

X-ray crystal structure analysis: formula Rb₂(CH₃OH)₃ (H₂O)· [(C₂₃H₁₅N₂O₄)₂Zn₂]·CH₃OH, M = 1214.60, yellow-orange crystal 0.30 × 0.30 × 0.05 mm, a = 12.944 (1), b = 13.320 (1), c = 15.608 (1) Å, α = 101.26 (1), β = 107.06 (1), γ = 99.84 (1)°, V = 2447.2 (3) ų, ρ_calcd = 1.648 gcm^-3, µ = 0.303 mm^-1, empirical absorption correction (0.464 ≤ T ≤ 0.863), Z = 2, triclinic, space group P1bar (No. 2), λ = 0.71073 Å, T = 198 K, ω and φ scans, 25862 reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.67 Å^-1, 11911 independent (R _int = 0.051) and 8202 observed reflections [I ≥ 2 σ(I)], 656 refined parameters, R = 0.047, wR ² = 0.100, max. residual electron density 0.72 (-0.57) eÅ^-3, hydrogen atoms are calculated and refined.

12c

Data set was collected with a Nonius Kappa CCD diffractometer, equipped with a rotating anode generator, COLLECT (Nonius B.V., 1998).

12d Data reduction, Denzo-SMN: Otwinowski Z. Minor W. Methods Enzymol.  1997,  276:  307 

12e Absorption correction, Denzo: Otwinowski Z. Borek D. Majewski W. Minor W. Acta Crystallogr., Sect. A  2003,  59:  228 

12f Structure solution, SHELXS-97: Sheldrick GM. Acta Crystallogr., Sect. A  1990,  46:  467 

12g Structure refinement: Sheldrick GM. SHELXL-97   Universität Göttingen; Germany: 1997. 

12h Graphics: Keller E. SCHAKAL   Universität Freiburg; Germany: 1997. 

12i

CCDC 294394 contains the supplementary crystallographic data for this paper. These data 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]].

13 Piguet C. Hopfgartner G. Williams AF. Bünzli J.-CG. J. Chem. Soc., Chem. Commun.  1995,  491 

See for example:

14a Piguet C. Hopfgartner G. Williams AF. Bünzli J.-CG. J. Chem. Soc., Chem. Commun.  1995,  491 

14b Petitjean A. Kyritsakas N. Lehn J.-M. Chem. Eur. J.  2005,  11:  6818 

14c Albrecht M. Fröhlich R. J. Am. Chem. Soc.  1997,  119:  1656