School of Pharmaceutical Sciences, Shandong University, 250100, Jinan, China.
School of Chemistry and Chemical Engineering, Shandong University, 250100, Jinan, China.
Nat Commun. 2019 Feb 4;10(1):559. doi: 10.1038/s41467-019-08473-x.
Catalytic enantioselective C-C bond forming process through cross-dehydrogenative coupling represents a promising synthetic strategy, but it remains a long-standing challenge in chemistry. Here, we report a formal catalytic enantioselective cross-dehydrogenative coupling of saturated ethers with diverse carboxylic acid derivatives involving an initial oxidative acetal formation, followed by nickel(II)-catalyzed asymmetric alkylation. The one-pot, general, and modular method exhibits wide compatibility of a broad range of saturated ethers not only including prevalent tetrahydrofuran and tetrahydropyran, but also including medium- and large-sized cyclic moieties and acyclic ones with excellent enantioselectivity and functional group tolerance. The application in the rapid preparation of biologically active molecules that are difficult to access with existing methods is also demonstrated.
通过交叉脱氢偶联实现的催化对映选择性 C-C 键形成过程代表了一种很有前途的合成策略，但它仍然是化学领域长期存在的挑战。在这里，我们报告了一种通过初始氧化缩醛形成，随后镍（II）催化不对称烷基化，实现饱和醚与各种羧酸衍生物的正式催化对映选择性交叉脱氢偶联。该一锅法、通用且模块化的方法不仅对包括常见的四氢呋喃和四氢吡喃在内的广泛的饱和醚具有广泛的相容性，而且对中等和大环以及具有优异对映选择性和官能团耐受性的无环醚也具有广泛的相容性。该方法还可用于快速制备现有方法难以获得的具有生物活性的分子。
