Building Three-Dimensional Complexity by Intramolecular 2-Aminoallyl Cation–Diene (4 + 3) Cycloaddition

IF 16.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Angewandte Chemie International Edition Pub Date : 2025-01-14 DOI:10.1002/anie.202423405
Lulu Shen, Tianzhu Qin, Chongling Jiao, Weiwei Zi
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Abstract

Reliable methods for rapidly constructing C(sp3)-rich three-dimensional polycycles are in high demand for organic synthesis and medicinal chemistry. Although there are various mature systems for synthesizing five- or six-membered polycycles, a catalytic platform for accessing diverse cycloheptanoid-containing polycyclic scaffolds is lacking. Herein, we describe a method for copper-catalyzed intramolecular 2-aminoallyl cation–diene (4 + 3) cycloaddition reactions. By using 1,3-diene-tethered ethynyl methylene cyclic carbamates as substrates, we were able to construct various cycloheptanoid-containing polycyclic scaffolds, which are present in many bioactive molecules. The cycloaddition products were rich in functionality that could undergo various chemical transformations. The synthetic utility of the method was illustrated by total synthesis of the natural products (±)-mint ketone and (±)-aphanamol I. Mechanistic studies indicated that the cycloadditions proceed via a concerted [4π + 2π] mechanism and that an endo-selective pathway is favored.
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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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