Total Synthesis of Dapholdhamine B and Dapholdhamine B Lactone

Guo, Lian-Dong; Hou, Jieping; Tu, Wentong; Zhang, Yan; Zhang, Yue; Chen, Louxi; Xu, Jing1

2019-07-24

10.1021/jacs.9b05641

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

The intriguing structural complexity and bioactivities of the Daphniphyllum alkaloids have long attracted much attention. Herein, we report the first and enantioselective total synthesis of Daphniphyllum alkaloid dapholdhamine B and its lactone derivative. The chemical structure of dapholdhamine B contains a unique aza-adamantane core skeleton and eight contiguous stereocenters, including three contiguous fully substituted stereocenters, which present a formidable synthetic challenge. This concise approach used to achieve the first synthesis of an azaadamantane natural product features a vinylogous Mannich reaction, an optimized alpha-bromo-alpha,beta-unsaturated ketone synthesis, a substrate-dependent intramolecular aza-Michael addition, a key annulation via amide activation, an S(N)2'-type lactonization, and a facile Horner-Wadsworth-Emmons reaction that converts the hemiacetal moiety to the corresponding homologated carboxylic acid.

SCI ; EI ; IC

英语

NI论文

通讯

SZSTI[JCYJ20170817110515599] ; SZSTI[KQJSCX20170728154233200]

Chemistry

Chemistry, Multidisciplinary

WOS:000477787400048

AMER CHEMICAL SOC

20193307322656

Addition reactions ; Alkaloids ; Amides ; Esters ; Ketones ; Metabolites

Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Organic Compounds:804.1

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen, Peoples R China

Guo, Lian-Dong,Hou, Jieping,Tu, Wentong,et al. Total Synthesis of Dapholdhamine B and Dapholdhamine B Lactone[J]. Journal of the American Chemical Society,2019,141(29):11713-11720.

Guo, Lian-Dong.,Hou, Jieping.,Tu, Wentong.,Zhang, Yan.,Zhang, Yue.,...&Xu, Jing.(2019).Total Synthesis of Dapholdhamine B and Dapholdhamine B Lactone.Journal of the American Chemical Society,141(29),11713-11720.

Guo, Lian-Dong,et al."Total Synthesis of Dapholdhamine B and Dapholdhamine B Lactone".Journal of the American Chemical Society 141.29(2019):11713-11720.