三氟甲基
立体中心
硼酸化
化学
三氟甲基化
立体专一性
有机化学
组合化学
立体化学
对映选择合成
芳基
催化作用
烷基
作者
Meganathan Nandakumar,Belén Rubial,Adam Noble,Eddie L. Myers,Varinder K. Aggarwal
标识
DOI:10.1002/anie.201912797
摘要
Stereogenic trifluoromethyl-substituted carbon centers are highly sought-after moieties in pharmaceutical and agrochemical discovery. Here, we show that lithiation-borylation reactions of 2-trifluoromethyl oxirane give densely functionalized and highly versatile trifluoromethyl-substituted α-tertiary boronic esters. The intermediate boronate complexes undergo the desired 1,2-rearrangement of the carbon-based group with complete retentive stereospecificity, a process that was only observed in non-polar solvents in the presence of TESOTf. Although the trifluoromethyl group adversely affects subsequent transformations of the α-boryl group, Zweifel olefinations provide trifluoromethyl-bearing quaternary stereocenters substituted with alkenes, alkynes and ketones.
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