Leaving Group Effects on the Selectivity of the Silylation of Alcohols: The Reactivity鈥揝electivity Principle Revisited

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• 作者：Pascal Patschinski ; Hendrik Zipse
• 刊名：Organic Letters
• 出版年：2015
• 出版时间：July 2, 2015
• 年：2015
• 卷：17
• 期：13
• 页码：3318-3321
• 全文大小：319K
• ISSN：1523-7052

文摘

TBS protection of primary alcohol naphthalen-1-ylmethanol (4a) and secondary alcohol 1-(naphthalen-1-yl)ethanol (4b) has been studied under various reaction conditions. The primary/secondary selectivity is largest in the comparatively slow Lewis base catalyzed silylation in apolar solvents and systematically lower in DMF. Lowest selectivities (and fastest reaction rates) are found for TBS triflate 1b, where only minor effects of solvent polarity or Lewis base catalysis can be observed.