Total Syntheses of Calyciphylline A-Type Alkaloids (-)-10-Deoxydaphnipaxianine A, (+)-Daphlongamine E and (+)-Calyciphylline R via Late-Stage Divinyl Carbinol Rearrangements

Zhang, Yan1,2,3,4; Chen, Yuye1,2,3,4; Song, Manrong1,2,3,4; Tan, Bin1,2,3,4; Jiang, Yujia1,2,3,4; Yan, Chongyuan1,2,3,4; Jiang, Yuyang1,2,3,4; Hu, Xinyue1,2,3,4; Zhang, Chengqian1,2,3,4; Chen, Wenqing1,2,3,4; Xu, Jing1,2,3,4

2022-08-01

10.1021/jacs.2c05957

Journal of the American Chemical Society   Impact Factor & Quartile

0002-7863

1520-5126

Among the famous Daphniphyllum alkaloids family, the calyciphylline A-type subfamily has triggered particular interest from the organic synthesis community in recent years. Here, we report divergent total syntheses of three calyciphylline A-type alkaloids, namely, (-)-10-deoxydaphnipaxianine A, (+)-daphlongamine E, and (+)-calyciphylline R. Our work highlights an efficient, divergent strategy via late-stage divinyl carbinol rearrangements, including an unprecedented oxidative Nazarov electrocyclization using an unfunctionalized tertiary divinyl carbinol and an unusual allylic alcohol rearrangement. A highly efficient "donor-acceptor " platinum catalyst was used for a critical nitrile hydration step. Moreover, the power of selective amide reductions has also been showcased by novel and classic tactics.

SCI

English

NI Journal Papers

First ; Corresponding

NSFC["21971104","22001114"] ; Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis[ZDSYS20190902093215877] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Guang-dong Innovative Program[2019BT02Y335]

Chemistry

Chemistry, Multidisciplinary

WOS:000849327700001

AMER CHEMICAL SOC

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
4.Southern Univ Sci & Technol, Shenzhen Key Lab Small Mol Drug Discovery & Synth, Shenzhen 518055, Peoples R China

Zhang, Yan,Chen, Yuye,Song, Manrong,et al. Total Syntheses of Calyciphylline A-Type Alkaloids (-)-10-Deoxydaphnipaxianine A, (+)-Daphlongamine E and (+)-Calyciphylline R via Late-Stage Divinyl Carbinol Rearrangements[J]. Journal of the American Chemical Society,2022.

Zhang, Yan.,Chen, Yuye.,Song, Manrong.,Tan, Bin.,Jiang, Yujia.,...&Xu, Jing.(2022).Total Syntheses of Calyciphylline A-Type Alkaloids (-)-10-Deoxydaphnipaxianine A, (+)-Daphlongamine E and (+)-Calyciphylline R via Late-Stage Divinyl Carbinol Rearrangements.Journal of the American Chemical Society.

Zhang, Yan,et al."Total Syntheses of Calyciphylline A-Type Alkaloids (-)-10-Deoxydaphnipaxianine A, (+)-Daphlongamine E and (+)-Calyciphylline R via Late-Stage Divinyl Carbinol Rearrangements".Journal of the American Chemical Society (2022).