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16b In this study, we obtain evidence for Nazarov cyclization for one class of annulation using cationic gold catalyst (Table 2 and Scheme 10). Since the other cyclizations share the same initial step, Nazarov cyclization is likely involved therein.
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16b In this study, we obtain evidence for Nazarov cyclization for one class of annulation using cationic gold catalyst (Table 2 and Scheme 10). Since the other cyclizations share the same initial step, Nazarov cyclization is likely involved therein.
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Treatment of allylSiMe3 and PPh3AuSbF6 did not generate PPh3Au(allyl) species through an allyl exchange; see ref 9c
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3Au(allyl) species through an allyl exchange; see ref 9c.
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6 (3 mol %) gave 1,4-dimethoxycyclopentyl product in satisfactory yield (88%) among these acidic catalysts. For detailed information, see Table S2 in Supporting Information.
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6 (3 mol %) gave 1,4-dimethoxycyclopentyl product in satisfactory yield (88%) among these acidic catalysts. For detailed information, see Table S2 in Supporting Information.
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1H NOE spectra, which are provided in Supporting Information.
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1H NOE spectra, which are provided in Supporting Information.
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Formation of the [4 + 2]-annulated product 4e from cis-dienal is proposed to follow the mechanism below. The key step involves an metal exchange between allylic cation and 2-siloxymethylallylsilane to give cation A″ and Au(I)-alkoxy species. This Au(I)-alkoxy species is highly nucleophilic to undergo nucleophilic addition to form species C″, and ultimately forms observed cycloadduct 4e.
-
Formation of the [4 + 2]-annulated product 4e from cis-dienal is proposed to follow the mechanism below. The key step involves an metal exchange between allylic cation and 2-siloxymethylallylsilane to give cation A″ and Au(I)-alkoxy species. This Au(I)-alkoxy species is highly nucleophilic to undergo nucleophilic addition to form species C″, and ultimately forms observed cycloadduct 4e.
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The annulated compounds 4b, 4c, 4f, and 4g were obtained as minor products according to the mechanism below.
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The annulated compounds 4b, 4c, 4f, and 4g were obtained as minor products according to the mechanism below.
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18O-enriched 1b and 6b are provided in Supporting Information.
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18O-enriched 1b and 6b are provided in Supporting Information.
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