Catalyst-Directed Divergent Catalytic Approaches to Expand Structural and Functional Scaffold Diversity via Metallo-Enolcarbene Intermediates
Catalyst-Directed Divergent Catalytic Approaches to Expand Structural and Functional Scaffold Diversity via Metallo-Enolcarbene Intermediates
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DOI：
10.1021/acscatal.1c01051
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发表时间：
2021-04-05
期刊：
影响因子：
12.9
通讯作者：
Doyle, Michael P.
中科院分区：
文献类型：
--
作者：
Dong, Kuiyong;Zheng, Haifeng;Doyle, Michael P.
报道了三种不同金属的不同产物在催化剂的引导下从相同的反应物中生成三种不同的产物。每种催化剂都将重氮乙酸烯和烯烃的金属-重氮卡宾途径引向特定的产物。这些反应包括：高选择性的分子间环丙化反应，完全由Dirhodium(II)羧酸盐催化，提供了大于20：1的非对映选择性和高达99%的ee；乙烯加成，随后的1，6-质子转移独立地在Au(I)或Cu(I)催化下进行，或[3+2]-环加成在铜(II)催化剂上进行；以及在银催化剂的存在下，与亚甲基二氢恶唑的C=N键直接环加成，然后重排生成多取代吡咯。烯丙基芳构化反应通过乙烯基加成选择性地从亚甲基二氢恶唑化合物中得到芳香恶唑衍生物，当1，6-质子转移不发生芳构化反应时，产物为[3+2]-环加成反应。这种依赖于催化剂的金属烯醇卡宾中间体与烯烃的形成展示了这种方法在以多样性为导向的合成方面的巨大潜力。
Catalyst-directed access to divergent products involving three different metals that exclusively form three different products from the same reactants is reported. Each catalyst directs an individual metallo-enolcarbene pathway from enoldiazoacetates and alkenes to a specific product. These include highly selective intermolecular cyclopropanation catalyzed exclusively by dirhodium(II) carboxylates, providing spiro-substituted dihydrooxazoles with greater than 20:1 diastereoselectivity and up to 99% ee; vinylogous addition with subsequent 1,6-proton transfer occurring independently with either Au(I) or Cu(I) catalysis or [3 + 2]-cycloaddition with a Cu(II) catalyst; and direct cycloaddition with the C=N bond of methylenedihydrooxazoles followed by rearrangement forming multiply substituted pyrroles in the presence of a silver catalyst. Allylic aromatization via vinylogous addition selectively delivers aromatic oxazole derivatives from methylenedihydrooxazoles, and when aromatization does not occur by 1,6-proton transfer, [3 + 2]-cycloaddition is the outcome. This catalyst-dependent formation of metallo-enolcarbene intermediates with alkenes demonstrates the tremendous potential of this approach to diversity-oriented-synthesis.