Asymmetric ortho-lithiation of 1,n-dioxa[n]paracyclophane derivatives for the generation of planar chirality |
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Authors: | Kazumasa Kanda Risa Hamanaka Kohei Endo Takanori Shibata |
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Institution: | 1. Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 65-504, 3-4-1, Okubo, Shinjuku, Tokyo 169-8555, Japan;2. Waseda Institute for Advanced Study, 1-6-1, Nishiwaseda, Shinjuku, Tokyo 169-8050, Japan |
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Abstract: | The asymmetric induction of planar chirality in 1,n-dioxan]paracyclophane derivatives via asymmetric ortho-lithiation is described. Enantioselective ortho-lithiation of unflippable 1,n-dioxan]paracyclophanes (n≤11) using sec-BuLi-(?)-sparteine at ?78 °C and subsequent treatment with electrophiles gave the corresponding planar-chiral monosubstituted paracyclophanes with excellent ee. Further lithiation of these compounds and treatment with electrophiles gave planar-chiral paracyclophanes with two different substituents. Dilithiation of unflippable 1,n-dioxan]paracyclophanes gave the corresponding C2-symmetrical disubstituted products with almost perfect ee. In the case of flippable 1,n-dioxan]paracyclophanes (n≥12), a stepwise reaction was required for the highly enantioselective formation of disubstituted products. |
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