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For catalytic reactions of other 3-siloxy-1,n-enynes, see: a) H. Menz, J. T. Binder, B. Crone, Tetrahedron 2009, 65, 1880-1888;
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For the related studies of benzylic alcohol substrates
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For the related studies of benzylic alcohol substrates, see: a) K. Mertins, I. Lovel, J. Kischel, A. Zapf, M. Beller, Adv. Synth. Catal. 2006, 348, 691-695;
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(b)A. S. K. Hashmi, L. Schwarz, P. Rubenbauer, M. C. Blanco, Adv. Synth. Catal. 2006, 348, 705-708;
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33645828418
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(a) Using 1:1 complex of the Au catalyst and AgSbF6 significantly lower the yield of the reaction. At this stage, it is unclear why the 2:1 complex gave higher yields of the product. It has been noted that that the chloro-bridged dinuclear gold complex is formed under this condition; A. S. K. Hashmi, M. C. Blanco, E. Kurpejović, W. Frey, J. W. Bats, Adv. Synth. Catal. 2006, 348, 709-713.
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73249138105
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note
-
As observed in the previous study for the siloxycyclization-[3,3]- sigmatropic pathway of 3-siloxy-1,6-enynes, the reaction gave no silyl ether 5a, even in the absence of any alcohol additives.(a)For the detailed procedure for the synthesis of the substrates, see the Supporting Information;(b) we also tried to investigate the reactivity of 5-methoxypent-3-en-yne derivative of 8. However, all our efforts to prepare the 5-methoxy-3-en-1-ynes from the corresponding alcohols proved troublesome, because of the poor stability of the corresponding alcohols under the reaction condition. The reaction conditions investigated include; (i) NaH/MeI in THF or DMF; ii) Ag2O/MeI in various solvents; iii) CH3OC=NHCCl3 with various Lewis acids.
-
-
-
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34
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73249145580
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note
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(a)Using other solvents (CH3CN, THF, EtOAc) significantly decreased the yield of the reaction; (b)we also examined various trialkylsilyl ethers: trimethylsilyl ethers provided the target in somewhat smaller yield, while triisopropylsilyl ethers significantly dropped the yield.
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-
-
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35
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73249139053
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note
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(a)The reaction performed in the presence of HF (up to 1 equiv) gave led to the complete decomposition of the starting material with no indication of the product formation; (b)the catalytic reaction under aerobic conditions (open flask condition) gave comparable results to the reactions under N2 atmosphere;(c)the reaction of the corresponding alcohol led to decomposition of the staring material with no indication of the product formation; also, we found out that the TES silyl ethers of tertiary alcohols are stable in general under the reaction condition-based on these experiments, alternative explanation on the cyclopentenone formation promoted by the initial desilylation and the subsequent cyclization can be reasonably excluded; (d) it should be noted that the scope of the reaction was strictly limited to the terminal alkynes; reaction of internal alkynes led to the decomposition of the staring material with no indication of formation of the cyclopentenones.
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-
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36
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0034638410
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17744400103
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For gold(I)-catalyzed approaches towards cyclopentenone synthesis, see: a) X. Shi, D. J. Gorin, F. D. Toste, J. Am. Chem. Soc. 2005, 127, 5802-5803;
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