98%
921
2 minutes
20
By utilizing an underexplored reaction mode of ,-cyclic azomethine imines, a catalyst-free [1+2+3] cycloaddition/N-N bond cleavage sequential reaction for accessing spiroindolines with -stereoselectivity was developed. On the basis of experimental results and DFT calculations, peroxide and ethereal solvent were identified to trigger the hydrogen abstraction of the unstable [1+2+3] cycloaddition adducts, followed by homolytic cleavage of the N-N bond and hydrogen absorption.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.orglett.2c01736 | DOI Listing |
J Am Chem Soc
August 2025
Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
Reactive intermediates that can promote nonintuitive bond disconnections underpin advancements in skeletal editing methodologies. Accordingly, a detailed understanding of their reactivity and its underlying mechanisms is central to progress in this space. Herein, we catalog and study the reactivity of nonstabilized cyclic isodiazene intermediates generated via the reaction of cyclic secondary amines with an anomeric amide reagent.
View Article and Find Full Text PDFJ Org Chem
June 2025
Department of Chemistry, Inha University, Incheon 22212, South Korea.
A selective synthesis of pyrazolidine-fused tetrahydroquinoline and C3-functionalized quinoline from -silyl enamine and ,-cyclic azomethine imine is presented, using [3 + 2] cycloaddition with varying reagent ratios. In this study, the ,-cyclic azomethine imine serves dual roles as both dipole and oxidant, with the latter being unprecedented. The dual role of ,-cyclic azomethine imine was confirmed through stepwise control reactions and deuterium-labeling studies.
View Article and Find Full Text PDFOrg Lett
June 2025
School of Life Sciences and Health Engineering, Jiangnan University, Wuxi 214122, China.
Presented herein is a catalyst-free cycloaddition of -quinamines and -quinols with ,-cyclic azomethine imines. A variety of 6/5/6/6-fused tetracyclic pyrazolidines featuring four contiguous stereocenters were facilely constructed via unprecedented [2 + 3] cycloaddition of -quinamines and -quinols. Such an intriguing cascade reaction pattern not only provided an atom- and step-economical strategy for the synthesis of multinitrogen polycyclic N-heterocycles containing a tertiary amine or alcohol group but also disclosed an unprecedented cycloaddition mode for -quinamines and -quinols as a two-atom synthon.
View Article and Find Full Text PDFCarbohydr Res
August 2025
Department of Chemistry, Bharathiyar College of Engineering and Technology, Union Territory of Puducherry, Karaikal, 609609, India. Electronic address:
The biocompatible nature of the chitosan biopolymer enables it to facilitate a wide range of organic transformations including chemical modification with some carbonyl compounds. Transition metal complexes namely [Ru(CS)4hy3mbd)(HO)].Cl [Ru(CS)2hybd)(HO)].
View Article and Find Full Text PDFOrg Lett
May 2025
Graduate School of Pharmaceutical Sciences, Nagoya University, Nagoya 464-8601, Japan.
Triggered by the reaction of an oxime ether with a rhodium carbenoid, nitrogen-containing three-dimensional frameworks were constructed from linear motifs via the intramolecular cycloaddition of -cyclic azomethine ylide. In this transformation, successive stereocenters containing quaternary carbons were formed, affording the corresponding tricyclic compounds in moderate-to-good yields. The utility of these products was demonstrated through several transformations.
View Article and Find Full Text PDF