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Protonated Breslow-type intermediates have been observed in NHC-mediated Baylis-Hillman reactions Hsu, J.-C.; Yen, Y.-H.; Chu, Y.-H. Tetrahedron Lett. 2004, 45, 4673-4676;
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Protonated Breslow-type intermediates have been observed in NHC-mediated Baylis-Hillman reactions (Hsu, J.-C.; Yen, Y.-H.; Chu, Y.-H. Tetrahedron Lett. 2004, 45, 4673-4676;
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33846925017
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and characterized crystallographically in the NHC-mediated addition of R-hydroxypro-pargylsilanes to aldehydes: Reynolds, T. E, Stern, C. A, Scheidt, K. A. Org. Lett. 2007, 9, 2581-2584
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and characterized crystallographically in the NHC-mediated addition of R-hydroxypro-pargylsilanes to aldehydes: Reynolds, T. E.; Stern, C. A.; Scheidt, K. A. Org. Lett. 2007, 9, 2581-2584.
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Trace acet al.dehyde required to initiate this process may be fomed via an acyl-imidazolium species normally postulated. As suggested by one of the reviewers, this same acyl-imidazolium species may also be responsible for the acylation of 5 or 6, and this represents a valid variation on either pathway a or pathway b.
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Trace acet al.dehyde required to initiate this process may be fomed via an acyl-imidazolium species normally postulated. As suggested by one of the reviewers, this same acyl-imidazolium species may also be responsible for the acylation of 5 or 6, and this represents a valid variation on either pathway a or pathway b.
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Compound 6 may also undergo O-acylation to give adduct 3 directly.
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Compound 6 may also undergo O-acylation to give adduct 3 directly.
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35
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0012380139
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Based on the proposed mechanism of benzil rearrangement in the presence of an NHC
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Based on the proposed mechanism of benzil rearrangement in the presence of an NHC: Lachmann, B.; Steinmaus, H.; Wanzlick, H. W. Tetrahedron 1971, 27, 4085-4090.
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Lachmann, B.1
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37
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This may also be attributed to the MeOAc requiring a reaction temperature of -20 instead of -78 °C as required for vinyl acetate
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This may also be attributed to the MeOAc requiring a reaction temperature of -20 instead of -78 °C as required for vinyl acetate.
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