The preparation of 3,3-difluoro-6-methylhept-5-en-2-one 1, a key intermediate for the synthesis of 4,4-difluoroterpenes, and applications in linalool and geraniol series are described. The process involves 1,1-difluoro-2-trimethylsilyoxypropene, an enol silyl ether prepared from acetyltrimethylsilane and trifluoromethyltrimethylsilane, and its reaction in situ with prenyl benzoate, under catalysis by trimethylsilyl trifluoromethanesulfonate. Optimized conditions leading to either the desired enol silyl ether or the unprecedented methyl(trifluoromethyl)trimethylsilyl carbinol 4 have been achieved. The prenylation of the enol silyl ether gives a 9/1 mixture of regioisomers, in favor of the expected ketone 1. Treatment of 1 with vinylmagnesium bromide leads to (+/-)-4,4-difluorolinalool 7. Reaction with the lithium enolate of ethyl diethylphosphonoacetate, and then LAH reduction, converts 1 to 4,4-difluorogeraniol 11, with complete stereoselectivity.

中文翻译：

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乙酰基三甲基硅烷，三氟甲基三甲基硅烷和异戊二烯基酯：三组分体系，用于合成单萜的宝石-二氟类似物。

描述了3,3-二氟-6-甲基庚-5-烯-2-酮1的制备，这是合成4,4-二氟萜烯的关键中间体，及其在芳樟醇和香叶醇系列中的应用。该方法涉及1，1-二氟-2-三甲基甲硅烷氧基丙烯，一种由乙酰基三甲基硅烷和三氟甲基三甲基硅烷制备的烯醇甲硅烷基醚，并在三甲基甲硅烷基三氟甲磺酸酯的催化下，与异戊烯基苯甲酸酯原位反应。已经获得了导致所需的烯醇甲硅烷基醚或空前的甲基（三氟甲基）三甲基甲硅烷基甲醇4的最佳条件。烯醇甲硅烷基醚的异戊烯基化得到区域异构体的9/1混合物，有利于预期的酮1。用乙烯基溴化镁处理1会生成（+/-）-4,4-二氟芳樟醇7。