A multifunctionalization of unactivated cyclic ketones via synergistic catalysis of copper and diarylamine for the direct synthesis of cyclic α-enaminone is reported for the first time. This reaction goes through oxidative α-amination, followed by a desaturation, and features mild reaction conditions, a broad substrate scope, and great functional group tolerance.
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http://dx.doi.org/10.1021/acs.orglett.8b00125 | DOI Listing |
Angew Chem Int Ed Engl
October 2024
Technical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis (IAS), State Key Laboratory of Material-Oriented Chemical Engineering, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing, 211816, China.
Although highly appealing for rapid access of molecular complexity, multi-functionalization of alkenes that allows incorporation of more than two functional groups remains a prominent challenge. Herein, we report a novel strategy that merges dipolar cycloaddition with photoredox promoted radical ring-opening remote C(sp)-H functionalization, thus enabling a smooth 1,2,5-trifunctionalization of unactivated alkenes. A highly regioselective [3+2] cycloaddition anchors a reaction trigger onto alkene substrates.
View Article and Find Full Text PDFJ Org Chem
November 2022
Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education, Hubei Key Laboratory of Catalysis and Materials Science, School of Chemistry and Materials Science, South-Central University for Nationalities, Wuhan, Hubei 430074, China.
The regioselective hydroamination of unactivated alkenes is a long-standing challenge in organic synthesis. Herein, we report a NiH-catalyzed proximal-selective hydroamination of unactivated alkenes with 8-aminoquinoline (AQ) as a bidentate auxiliary and anthranils as aminating reagents. A wide range of primary aryl amines bearing an -carbonyl group were installed in both terminal and internal unactivated alkenes, delivering a variety of valuable β- and γ-amino acid building blocks, respectively, with excellent regiocontrol.
View Article and Find Full Text PDFNat Commun
July 2022
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
Selective deuteration of unactivated C(sp)-H bonds is a highly attractive but challenging subject of research in pharmaceutical chemistry, material science and synthetic chemistry. Reported herein is a practical, highly selective and economical efficient hydrogen/deuterium (H/D) exchange of unactivated C(sp)-H bonds by synergistic photocatalysis and hydrogen atom transfer (HAT) catalysis. With the easily prepared PMP-substituted amides as nitrogen-centered radical precursors, a wide range of structurally diverse amides can undergo predictable radical H/D exchange smoothly with inexpensive DO as the sole deuterium source, giving rise to the distal tertiary, secondary and primary C(sp)-H bonds selectively deuterated products in yields of up to 99% and excellent D-incorporations.
View Article and Find Full Text PDFChem Soc Rev
April 2022
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, P. R. China.
C-H functionalization has been emerging as a powerful method to establish carbon-carbon and carbon-heteroatom bonds. Many efforts have been devoted to transition-metal-catalyzed direct transformations of C-H bonds. Metal carbenes generated from transition-metal compounds and diazo or its equivalents are usually applied as the transient reactive intermediates to furnish a catalytic cycle for new C-C and C-X bond formation.
View Article and Find Full Text PDFOrg Lett
August 2020
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu 215123, China.
Herein we describe an efficient distal ipso-migration of - and -containing heteroaryls and the radical heteroarylation of unactivated alkenes. The migration is triggered by various fluoroalkyl radicals, leading to valuable multifunctionalized ketones. The comparisons of migratory aptitude for -/-containing heteroaryls are comprehensively investigated.
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