期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 80, 期 17, 页码 8727-8738出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.5b01540
关键词
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资金
- IRC
- Science Foundation Ireland
Highly regioselective benzylic metalations in hydrocarbon solvent have been achieved at rt and 0 degrees C using a mixed-metal Li/K-TMP amide comprised of KOtBu, BuLi, and 2,2,6,6,-tetramethylpiperidine (TMP(H)). Mixing of KOtBu, BuLi, and TMP(H) in heptane gave a solution of the base mixture which when used in deuterium labeling experiments confirmed the requirement of the three reagent components for both reactivity and selectivity. The reaction protocol is operationally straightforward and found to be applicable to a broad range of substrates. Upon generation of the metalated products, they are reacted in heptane at ambient temperature in a variety of synthetically useful ways. Illustrated examples include generation of the benzyltrimethylsilanes and alpha,alpha-bis(trimethylsilyl)toluenes reagents, which are bench-stable surrogates of benzyl anions and alpha-silyl carbanions utilized for nudeophilic addition and Peterson olefination reactions. Direct C-C couplings mediated by 1,2-dibromoethane provided entries into bibenzyls and [2.2]metacyclophanes. Comparison of reaction outcomes with the same reactions carried out in THF at -78 degrees C showed no negative effects for conducting the reactions under these milder more user-friendly conditions.
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