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For a small review with Au as the catalyst, see
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For a small review with Au as the catalyst, see: N. Marion, S. P. Nolan, Angew. Chem. 2007, 119, 2806-2809;
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Recent computational studies suggest that both Au-mediated pathways could be interconnected, see
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Recent computational studies suggest that both Au-mediated pathways could be interconnected, see: A. Correa, N. Marion, L. Fensterbank, M. Malacria, S. P. Nolan, L. Cavallo, Angew. Chem. 2008, 120, 730-733;
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Herein, an interesting chirality transfer from an optically active propargyl pivaloate was postulated to proceed by the cyclic oxonium ion similar to mechanisms proposed for such conservation of stereochemical information in other cases such as: a A. Fürstner, P. Hannen, Chem. Eur. J. 2006, 12, 3006-3019;
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Herein, an interesting chirality transfer from an optically active propargyl pivaloate was postulated to proceed by the cyclic oxonium ion similar to mechanisms proposed for such conservation of stereochemical information in other cases such as: a) A. Fürstner, P. Hannen, Chem. Eur. J. 2006, 12, 3006-3019;
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In a subsequent calculation, a helical intermediate was found to retain the stereochemical information of the starting material: c O. N. Faza, C. S. López, R. Álvarez, A. R. de Lera, J. Am. Chem. Soc. 2006, 128, 2434-2437
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57749101184
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For the preparation of new compounds and additional experimental details, see the Supporting Information
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For the preparation of new compounds and additional experimental details, see the Supporting Information.
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36
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57749115929
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3 and MeOH as solvent, substrate 1 f reacted through a 1,2-acetate shift and solvolysis of the cyclopropane unit to give a methoxy adduct: (Chemical Equation Presented)
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3 and MeOH as solvent, substrate 1 f reacted through a 1,2-acetate shift and solvolysis of the cyclopropane unit to give a methoxy adduct: (Chemical Equation Presented)
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39
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57749091791
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The absolute configurations of (R)-8k and (R)-19e were determined by comparing the vibrations of the measured ROA spectra with those of the theoretical spectra, calculated at the B97-1/pc-2 level with the Gaussian program. See: a)W. Hug, Continuum Solvation Models in Chem. Physics 2007, 220-237;
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The absolute configurations of (R)-8k and (R)-19e were determined by comparing the vibrations of the measured ROA spectra with those of the theoretical spectra, calculated at the B97-1/pc-2 level with the Gaussian program. See: a)W. Hug, Continuum Solvation Models in Chem. Physics 2007, 220-237;
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b) ROA calculations at the TDHF/DPS level was carried out with the Dalton program: G. Zuber, W. Hug, J. Phys. Chem. A 2004, 108, 2108-2118;
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for applications see: d) M. A. Lovchik,G. Frater, A. Goeke, W. Hug, Chem. Biodiversity 2008, 5, 126-139;
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57749108212
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A diastereomeric ratio of 6:4 would account for a chirality transfer of a maximum 20%ee.
-
A diastereomeric ratio of 6:4 would account for a chirality transfer of a maximum 20%ee.
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46
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0002846538
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For a general review on nonclassical cations, see
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27744598795
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Species 3k (see also 3 in Scheme 2) could be most likely represented as the E configured vinyl gold intermediates. Nevertheless, Z isomer has been postulated to be plausible, being generated by anchimeric assistance allowing the cyclization with minimal steric hindrance, see: E. Soriano, J. Marco-Contelles, J. Org. Chem. 2005, 70, 9345-9353.
-
Species 3k (see also 3 in Scheme 2) could be most likely represented as the E configured vinyl gold intermediates. Nevertheless, Z isomer has been postulated to be plausible, being generated by anchimeric assistance allowing the cyclization with minimal steric hindrance, see: E. Soriano, J. Marco-Contelles, J. Org. Chem. 2005, 70, 9345-9353.
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