Kinetic and Thermodynamic Control of Aldolization in Higher Order Polyquinane Systems

References

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• Although the calculations are for the gas phase, the only part of the calculation that is phase dependent is the electrostatic energy (dipole energy). Placing the molecules into a non-interacting solvent of dielectric constant D would result in a reduction of the dipole energy (dipole energy/D), but by almost the same amount for each isomer. These differences are not significant. For solvents offering specific interactions with the solute, a dependence on steric effects might surface and be linked to the specific configuration at the alkoxide-substituted carbon atom
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• The authors are inbedted to Drs. Judith C. Gallucci and Yeh-Leh Hsu of our departmental X-ray crystallographic facility for the crystal structure analyses of these compounds
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• 7: lH NMR (300 MHz, CDCl3) δ 4.48 (m, 1 H), 3.88 (s, 4 H), 2.70–2.45 (m, 3 H), 2.23–1.5 (series of m, 9 H), 0.84 (s, 9 H), 0.037 (s, 3 H), 0.021 (s, 3 H); 8: δ 4.29 (m, 1 H), 3.87 (s, 4 H), 2.51 (s, 1 H), 2.5–2.0 (m, 7 H), 1.77 (m, 1 H), 1.64 (m, 2 H), 1.43 (m, 1 H), 0.85 (s, 9 H), 0.062 (s, 3 H), 0.041 (s, 3 H); 9: δ 3.92 (m, 1 H), 3.90–3.80 (m, 4 H), 2.44 (d, J = 3.2 Hz, 1 H), 2.4–2.3 (m, 1 H), 2.1–1.75 (m, 6 H), 1.6–1.4 (m, 4 H), 0.873, 0.871 (2 s, total 9 H), 0.068 (s, 3 H), 0.027 (s, 3 H); 10: δ 4.00 (m, 1 H). 3.95–3.80 (m, 4 H), 2.69 (t, J = 10.3 Hz, 1 H), 2.51 (d, J = 4.8 Hz, 1 H), 2.43–2.36 (m, 1 H), 2.16–2.10 (m, 3 H), 1.95–1.75 (m, 2 H), 1.70–1.43 (series of m, 4 H), 0.88 (s, 9 H), 0.046 (s, 3 H), 0.033 (s, 3 H)
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• Treatment of 2 with dilute HCl in tetrahydrofuran (25°C, 14 h) affords the deketalized derivatives of 7 (64%), 9 (30%), and 10 (6%). No congener of 8 was observed. Interestingly, the epimers that carry the hydroxyl group on the concave surface are favored under these conditions, perhaps to gain advantage of intramolecular hydrogen bonding
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