Liu Xiang-Shuai, Li Yao, Li Xin
State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China.
Org Lett. 2021 Dec 3;23(23):9128-9133. doi: 10.1021/acs.orglett.1c03453. Epub 2021 Nov 15.
A highly efficient asymmetric 1,2-allylation reaction of β,γ-unsaturated α-ketoesters was realized by using a Bi(OAc)/chiral phosphoric acid catalyst system under mild conditions. Meanwhile, using this combined strategy of enantioselective 1,2-allylation and subsequent anionic oxy-Cope rearrangement, the asymmetric formal 1,4-allylation reaction was achieved by a one-pot process. These reactions offer rapid access to an array of homoallylic tertiary alcohols and γ-allyl-α-ketoesters with good yields and excellent enantioselectivities. Density functional theory calculations were conducted to interpret the high enantioselectivity.
在温和条件下，通过使用Bi(OAc)/手性磷酸催化剂体系实现了β,γ-不饱和α-酮酯的高效不对称1,2-烯丙基化反应。同时，利用这种对映选择性1,2-烯丙基化和随后的阴离子氧杂-Cope重排的联合策略，通过一锅法实现了不对称形式的1,4-烯丙基化反应。这些反应能够快速获得一系列具有良好产率和优异对映选择性的高烯丙基叔醇和γ-烯丙基-α-酮酯。进行了密度泛函理论计算以解释高对映选择性。
