Stability, Kinetic, and Mechanistic Investigation of 1,8-Self-Immolative Cinnamyl Ether Spacers for Controlled Release of Phenols and Generation of Resonance and Inductively Stabilized Methides

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• 作者：Siddharth S. Matikonda ; Jessica M. Fairhall ; Joel D. A. Tyndall ; Sarah Hook ; Allan B. Gamble
• 刊名：Organic Letters
• 出版年：2017
• 出版时间：February 3, 2017
• 年：2017
• 卷：19
• 期：3
• 页码：528-531
• 全文大小：329K
• ISSN：1523-7052

文摘

Three cinnamyl ether spacers (non-methyl, α-methyl, and γ-methyl) for caging of phenols have been synthesized and are physiologically stable. When triggered, the γ-methyl spacer releases phenols (pK_a 7.8 and 9.8) with a t_1/2 < 30 s and <2 min in aqueous and aqueous–organic solvent, respectively. The α-methyl spacer releases a phenol (pK_a 7.8) with a t_1/2 = 27 and 54 min. For the γ-methyl spacer, the results suggest the presence of a resonance and inductively stabilized aza-cinnamyl methide.