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It was confirmed by the DLS measurements of the reaction solutions that no ruthenium clusters (detection limit: 0.6 nm) were detected during the dehydrosilylation.
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It was confirmed by the DLS measurements of the reaction solutions that no ruthenium clusters (detection limit: 0.6 nm) were detected during the dehydrosilylation.
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41
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67549109928
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For solid carboxylic acids, toluene or 1,4-dioxane was used as a solvent
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For solid carboxylic acids, toluene or 1,4-dioxane was used as a solvent.
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42
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67549112789
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Lee and co-workers have reported the efficient synthesis of siloxacycles from terminal alkenyl alcohols and alkynylsilanes.[4k] The synthesis consists of two consecutive reactions of silylation of the terminal alkenyl alcohols with alkynylsilanes followed by the intramolecular methathesis, and [RuCl2(p-cymene)]2 is used for the former silylation.[4k] Although the silylation of alkenyl and alkynyl alcohols is reported in the literature, the applicability to aliphatic and benzylic alcohols as well as carboxylic acids is not mentioned.[4k
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[4k]
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2 with respect to the corresponding silyl ethers were also formed.
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2 with respect to the corresponding silyl ethers were also formed.
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44
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0001721984
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45
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0034614043
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A similar mechanism has been reported for the hydrolytic oxidation of silanes with water: a M. Lee, S. Ko, S. Chang, J. Am. Chem. Soc. 2000, 122, 12011;
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A similar mechanism has been reported for the hydrolytic oxidation of silanes with water: a) M. Lee, S. Ko, S. Chang, J. Am. Chem. Soc. 2000, 122, 12011;
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46
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47
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67549119934
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S= 19.9 min, DAICEL CHIRALCEL ODH, 0.46 cm φ×0.25 cm, eluent: n-hexane) with a CD-detector: S. Shinke, T. Tsuchimoto, Y. Kawakami, Silicon Chem. 2005, 3, 243.
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S= 19.9 min, DAICEL CHIRALCEL ODH, 0.46 cm φ×0.25 cm, eluent: n-hexane) with a CD-detector: S. Shinke, T. Tsuchimoto, Y. Kawakami, Silicon Chem. 2005, 3, 243.
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48
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67549138143
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Under the conditions described in Eq. (6) (1.5 equivalents of 4b with respect to 2f), the reaction rate was very slow and the corresponding silyl ether was obtained in 30% yield after 48 h. In this case, the ee values of the product were almost unchanged during the reaction (84-88%ee).
-
Under the conditions described in Eq. (6) (1.5 equivalents of 4b with respect to 2f), the reaction rate was very slow and the corresponding silyl ether was obtained in 30% yield after 48 h. In this case, the ee values of the product were almost unchanged during the reaction (84-88%ee).
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49
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67549102766
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2 and excess amounts of alcohols. Therefore, the optical purity of the R-isomer 5s was decreased by the transetherification (racemization)in the presence of large excess amounts of 4b [Eq. (7)].
-
2 and excess amounts of alcohols. Therefore, the optical purity of the R-isomer 5s was decreased by the transetherification (racemization)in the presence of large excess amounts of 4b [Eq. (7)].
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