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There has been a recent discussion on the role of Brønsted acids in homogenous transition metal-catalyzed reactions. For the most relevant references, see: (a) Hashmi, A. S. K. Catal. Today 2007, 122, 211.
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The more facile propargyl-allenyl isomerization for selenoalkynones is well supported by notable cycloisomerization of 16a under thermal conditions in the absence of base and Cu-catalyst (Table 3, entry 4).
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It should be noted that involvement of any possible ionization pathways during cycloisomerization of thioalkynones 12 was ruled out by the absence of scrambling for alkyl- and arylthio- groups in crossover experiment
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It should be noted that involvement of any possible ionization pathways during cycloisomerization of thioalkynones 12 was ruled out by the absence of scrambling for alkyl- and arylthio- groups in crossover experiment.
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This is in striking contrast to cycloisomerization of alkynyl imines and ketones, where significant loss of deuterium was observed; see refs 9 and 12.
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Decrease in regioselectivity of deuterium vs bromine migration is explained by the isotope effect analogous to that observed by Hashmi in the Pd-catalyzed cycloisomerization of allenyl ketones; see ref 7s.
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For examples of 1,2-shift in vinyl cations, see: (a) Capozzi, G.; Lucchini, V.; Marcuzzi, F.; Melloni, G. Tetrahedron Lett. 1976, 17, 717.
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See also ref 7q.
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20 from 2-thio- to 3-thiofuran after assembly of the furan core.
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20 from 2-thio- to 3-thiofuran after assembly of the furan core.
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The observed migratory aptitude trends (Ph vs. Et, and Ph vs. Me) do not correspond to diose reported in literature for 1,2-alkyl migration to carbenoid center. See, for example: (a) Philip, H.; Keating, J. Tetrahedron Lett. 1961, 2, 523.
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