Song De-Xin, Song Yu-Hua, Huang Heng-Hua, Huang Xiao-Yan, Yang Fang, Ji Kegong, Chen Zi-Sheng
Shaanxi Key Laboratory of Natural Products & Chemical Biology, College of Chemistry and Pharmacy, Northwest A&F University, Yangling 712100, Shaanxi, P. R. China.
Org Lett. 2024 Sep 20;26(37):7920-7925. doi: 10.1021/acs.orglett.4c02947. Epub 2024 Sep 9.
A cooperative Rh(II)/Pd(0) dual-catalysis strategy that enabled divergent reactions of α-diazo 1,3-dicarbonyl compounds with allylic carbonates involving ketene versus carbene intermediates is described. The efficient synthesis of α-quaternary allylated β-keto-esters was accomplished by the Rh(II)/Pd(0) dual-catalysis allylic alkylation of α-diazo 1,3-dicarbonyl compounds. Alternatively, an unprecedented (1+4) annulation of α-diazo 1,3-dicarbonyl compounds with 2-(hydroxymethyl)allyl carbonates via Rh(II)/Pd(0) dual catalysis was also successfully developed, affording a wide variety of α-quaternary tetrahydrofurans in good to high yields.
描述了一种协同的铑（II）/钯（0）双催化策略，该策略能够使α-重氮1,3-二羰基化合物与烯丙基碳酸酯发生不同反应，涉及乙烯酮与卡宾中间体。通过铑（II）/钯（0）双催化烯丙基烷基化反应，实现了α-季碳烯丙基化β-酮酯的高效合成。此外，还成功开发了一种前所未有的α-重氮1,3-二羰基化合物与2-（羟甲基）烯丙基碳酸酯通过铑（II）/钯（0）双催化的（1+4）环化反应，以良好至高产率得到了多种α-季碳四氢呋喃。
