The first example of (3+3)-annulation of two different three-membered rings is reported herein. Donor-acceptor cyclopropanes in reaction with diaziridines were found to afford perhydropyridazine derivatives in high yields and diastereoselectivity under mild Lewis acid catalysis. The disclosed reaction is applicable for the broad substrate scope and exhibits an excellent functional group tolerance.
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http://dx.doi.org/10.1002/anie.201805258 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
New York University, Chemistry, 29 Washington Place, RM 10001, 10003, New York, UNITED STATES OF AMERICA.
Herein, we report a Lewis acid-mediated ring expansion of donor-acceptor cyclopropanes (DACs) to substituted azetidines via nucleophilic nitrogen group transfer from readily accessible iminoiodinane. This protocol operates under mild, transition-metal-free conditions, and showcases excellent chemoselectivity, along with broad functional group tolerance. We report for the first time that challenging alkyl donor-acceptor cyclopropanes can undergo ring expansion leading to aliphatic azetidines without relying on external oxidants or precious transition-metal catalysts.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
J Am Chem Soc
January 2025
State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Fuzhou 350100, China.
Catalytic asymmetric transformation of donor-acceptor cyclopropanes (DACs) has been proven to be a highly valuable and robust strategy to construct diverse types of enantioenriched molecules. However, the use of 1,1,2,2-tetrasubstituted DACs to form products bearing quaternary stereocenters remains a long-term unsolved challenge. Here, we report the copper-catalyzed asymmetric aminative ring opening of tetrasubstituted alkynyl DACs that delivers a myriad of α-tertiary amines with high levels of enantioselectivities.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Department of Chemistry and Chemical Biology, Indian Institute of Technology (ISM) Dhanbad, Jharkhand, 826004, India.
J Org Chem
December 2024
School of Chemistry and Chemical Engineering, Yangzhou University, 180 Siwangting Street, Yangzhou 225002, P. R. China.
Efficient synthesis of highly functionalized cyclopentenols with an exocyclic Z double bond was investigated via a (3 + 2) annulation reaction of 2-aroyl-D-A (donor-acceptor) cyclopropanes with alkynoates in the presence of DABCO. This synthetic approach featured a wide range of readily available 2-aroyl-substituted D-A cyclopropanes with diverse functional groups, densely substituted cyclopentenols with two stereogenic centers and an exocyclic double bond in a highly stereocontrolled manner and had operationally simple and mild reaction conditions.
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