This work reports cascade cyclization between 1-allenyl-2-alkynylbenzenes and nitrosoarenes. When these two components reacted alone under N, N,O-functionalized indane-fused isoxazolidines were obtained selectively. DFT calculations verify that this reaction sequence involves unprecedented nitrone/alkyne cycloadditions, followed by diradical rearrangement.
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http://dx.doi.org/10.1021/acs.orglett.2c03884 | DOI Listing |
Org Lett
December 2024
National Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang 330022, China.
We have developed a glycosyl radical-based synthesis of -alkyl glycosides through a deoxygenative Giese addition-reduction-cyclization cascade, in which readily available 1-hydroxy carbohydrates serve as precursors for glycosyl radicals and aryl alkenes function as radical acceptors. This reaction not only provides an effective method for accessing a previously underexplored class of functionalized cyclopropanes but also enhances the application of Giese addition in the synthesis of -alkyl glycosides by derivatizing the radical intermediate generated through polar cyclization to yield a cyclopropane.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
Department of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, P. R. China.
In light of the extensive applications of sulfur-containing heterocyclic compounds in drug discovery, agrochemicals, and advanced materials, the construction of complex sulfur-containing molecular scaffolds has flourished in recent years. There is a profound interest in synthetic methods for forming carbon-sulfur bonds. Regarding this, transition metal (TM)-catalyzed C-H bond activation has emerged as a valuable means for the rapid formation of C-S bonds, although it is comparatively less explored than C-N or C-C bonds.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry, New York University, New York, New York 10003, United States.
Complexity-generating reactions that access three-dimensional products from simple starting materials offer substantial value for drug discovery. While oxygen-containing heterocycles frequently feature unique, nonaromatic architectures such as spirocyclic rings, exploration of these chemical spaces is limited by conventional synthetic approaches. Herein, we report a copper-catalyzed annulation and alkene transposition cascade reaction that enables a modular preparation of complex, spirocyclic ethers from readily available alkenol substrates via a copper-catalyzed annulation and transannular 1,5-hydrogen atom transfer-mediated C-H functionalization.
View Article and Find Full Text PDFJ Org Chem
December 2024
Key Laboratory of Biocatalysis & Chiral Drug Synthesis of Guizhou Province, School of Pharmacy, Zunyi Medical University, Zunyi 563003, P. R. China.
A convenient electrochemical oxidative cascade cyclization of alkenes equipped with pendant alcohols with general nucleophiles was developed. Using readily available diarylmethanimine and carboxylic acids as nucleophilic sources, a broad range of internal alkene and terminal alkene substrates could produce RCO- and ArCN-functionalized -heterocycles in moderate to high yields without the requirement for external oxidants and metals. These resulting products can subsequently be hydrolyzed to yield valuable NH- and OH-functionalized tetrahydrofurans and tetrahydropyranes under mild conditions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
University of Western Ontario: Western University, Chemistry, CANADA.
The development of polymers from renewable resources is a promising approach to reduce reliance on petrochemicals. In addition, depolymerization is attracting significant attention for the breakdown of polymers at their end-of-life or to achieve specific stimuli-responsive functions. However, the design of polymers incorporating both of these features remains a challenge.
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