A reductive dicarbofunctionalization reaction of alkenes has been developed and applied to the preparation of substituted carbo- and heterocycles. The reaction conditions avoid the use of air-sensitive organometallic reagents, and are compatible with a broad range of bromo-electrophiles and a wide variety of substituents to give cyclic products in excellent yields.
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http://dx.doi.org/10.1039/c8cc00358k | DOI Listing |
Org Lett
October 2024
School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, P. R. China.
An enantioselective 1,2-dicarbofunctionalization of vinyl (hetero)arenes with alkyl bromides and aryl bromides through nickel/photoredox catalysis is described. This three-component enantioselective domino alkyl arylation of vinyl (hetero)arenes could generate a diverse array of enantioenriched 1,1-diaryl(heteroaryl)alkanes with good to excellent yields (up to 88%) and high enantioselectivities (up to 99% ). This transformation could proceed well under mild conditions with excellent chemo- and regioselectivity due to the avoidance of the use of air- and moisture-sensitive organometallic reagents and stoichiometric metal reductants.
View Article and Find Full Text PDFOrg Lett
October 2024
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610068, People's Republic of China.
A three-component reductive 1,4-dicarbofunctionalization of 1,3-dienes with aziridines and (het)aryl electrophiles was realized. The combination of Ni catalysis with Mn powder as a final reductant enables the direct formation of a Csp-Csp and a Csp-Csp bond at one time. This protocol afforded a convenient approach to the synthesis of β-arylethylamines bearing various functionals and heterocyclic groups.
View Article and Find Full Text PDFJ Am Chem Soc
September 2024
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
The Wacker and Wacker-type reactions are some of the most fundamental and powerful transformations in organic chemistry for their ability to efficiently produce valuable chemicals. Remarkable progress has been achieved in asymmetric oxy/aza-Wacker-type reactions; however, asymmetric Wacker-type dicarbofunctionalization remains underdeveloped, especially for the concurrent construction of two stereocenters. Herein, we report a Pd/Cu-cocatalyzed enantio- and diastereodivergent Wacker-type dicarbofunctionalization of alkene-tethered aryl triflates with imino esters.
View Article and Find Full Text PDFOrg Lett
May 2024
Key Laboratory of Precision and Intelligent Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, People's Republic of China.
A binary Ni/Eu catalytic system has been developed, which enables an efficient reductive dicarbofunctionalization of unactivated alkenes with alkyl halides and malononitriles. The combination of Ni electron-shuttle catalysis with Eu(OTf), a non-redox-type Lewis acid, effectively activates the iminyl radicals, enabling the direct formation of the C(sp)-C(sp) bond and β-ketonitrile functionality across a variety of C═C double bonds. This reaction allows for the expedient synthesis of densely functionalized cyclic β-ketonitriles bearing all-carbon quaternary centers.
View Article and Find Full Text PDFAcc Chem Res
November 2023
Department of Chemistry, National University of Singapore, 4 Science Drive 2, Republic of Singapore, 117544.
ConspectusEfficient construction of ubiquitous carbon-carbon bonds between two electrophiles has garnered interest in recent decades, particularly if it is mediated by nonprecious, first-row transition metals. Reductive coupling has advantages over traditional cross-coupling by obviating the need for stoichiometric air- and moisture-sensitive organometallic reagents. By harnessing transition metal-catalyzed reductive coupling as a powerful tool, intricate molecular architectures can be readily assembled through the installation of two C-C bonds across π systems (alkenes/alkynes) via reaction with two appropriate electrophiles.
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