期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 135, 期 43, 页码 16054-16057出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja409100y
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资金
- EPSRC
- European Research Council (ERC) [246785]
- Spanish Ministerio de Ciencia e Innovacion (FPU fellowship)
- EPSRC [EP/E052185/1, EP/I038071/1, EP/K03927X/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/I038071/1, EP/K03927X/1, EP/E052185/1] Funding Source: researchfish
Simple, secondary 2,4,6-triisopropyl benzoates (TIB esters) and secondary dialkyl N,N-diisopropyl carbamates have been reported to be resistant to deprotonation by strong bases. We have found that the combination of sBuLi (1.6 equiv) and TMEDA (6 equiv) in CPME at -60 degrees C enables deprotonation of unactivated secondary dialkyl TIB esters, but not the carbamates. These carbanions were reacted with a range of neopentyl boronic esters which, after 1,2-metalate rearrangement and oxidation, gave a range of tertiary alcohols in high yield and universally high er. Further functional group transformations of the tertiary boronic esters were demonstrated (conversion to quaternary centers, C-tertiary amines) together with application of the methodology to the synthesis of the simplest unbranched hydrocarbon bearing a quaternary center, (R)-4-ethyl-4-methyloctane, validating the synthetic utility of the methodology.
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