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note
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For details on reaction conditions see the Supporting Information.
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85028161996
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note
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Other bases with different features were tested (see page 3 in the Supporting Information). Only weak bases such as 2,6-dichloropyridine or norbornene resulted in full conversion, although less efficiently than ttbp to generate 2a. Less hindered or more basic ones did not result in full conversion. It is likely that the role of the base implies a subtle balance between the catalyst reactivity and the decomposition of the product. Overall, the use of the base results in a robust and reproducible reaction and higher yields. Interestingly, in some cases it was possible to monitor by the formation and fast decomposition of the product (by TLC) in the absence of the base.
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2 among them. For both the consumption of 1a occurred after reacting for 1 h and 4 h, respectively. The formation of 2a was evident by NMR analysis of the crude reaction mixtures but, in both cases additional products were present.
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45
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note
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For the synthesis and characterization of 1 and 2, including copies of the spectra, and mechanistic details, see the Supporting Information.
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46
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85028139445
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note
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1a nicely isomerizes to 2a in high yield, however, competitive formation of minor amounts of an alternative cyclization product, likely from oxygen getting involved as nucleophile, was noticed in the crude reaction mixture. These two products turned out to be difficult to separate and 2a was isolated in moderate yield. For the catalytic conversion of 1b into 2b, no evidence of alternative by-product was found by NMR analysis of the corresponding crude reaction mixture.
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47
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1-(bromoethynyl)-2-(methoxymethyl)benzene, an analogue of 1d, was tested under the same reaction conditions. No cyclization was observed and the starting material was recovered essentially unaltered. The cyclization of 1-(iodoethynyl)-2-(1-methoxyethyl)cyclohex-1-ene resulted in a sluggish reaction where no cycloisomerization was observed.
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6 and ttbp (10 mol%) in DCE at 80 8C, for 0.5 h, 2g was isolated in 53% yield (e.r. 81:19). This result might provide additional evidence for the concerted insertion step.
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