We report a Cu(II)-catalyzed cyclization/coupling of alkenyl aldimines with arylzinc reagents to create indole-3-diarylmethane derivatives (Sapkota et al. , DOI: 10.26434/chemrxiv-2022-d6qn). The current reaction provides a unified modular route from readily available starting materials to indole-3-diarylmethanes in which all three arene cores can be decorated with differential functional substitutions on demand. Since the cyclization/coupling of alkenyl aldimines is unknown to date, the current method widens the scope with regard to both the substrate and product diversity for this class of reaction.
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http://dx.doi.org/10.1021/acs.orglett.2c02531 | DOI Listing |
J Org Chem
May 2024
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland.
An unprecedented DDQ-mediated oxidative aromatization of 2-bezylidene-dihydrofurans yielding 2-alkenyl-furans is disclosed. Integration of this transformation with a prior Pd-catalyzed reaction of α-propargylic-β-ketoesters and (hetero)aryl halides into a one-pot cascade process opens a direct modular route to highly substituted 2-vinyl-furans. Experimental and computational studies reveal that the crucial step of the oxidative-aromatization involves facile hydride transfer from the dihydrofuran ring to the O-center of DDQ.
View Article and Find Full Text PDFOrg Lett
August 2022
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
We report a Cu(II)-catalyzed cyclization/coupling of alkenyl aldimines with arylzinc reagents to create indole-3-diarylmethane derivatives (Sapkota et al. , DOI: 10.26434/chemrxiv-2022-d6qn).
View Article and Find Full Text PDFJ Am Chem Soc
March 2022
Sauvage Center for Molecular Sciences, Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education), and College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, China.
An enantioselective nickel-catalyzed intramolecular reductive cross-coupling of C(sp) electrophiles and cyano groups is reported. Enantioenriched CN-containing all-carbon quaternary stereocenters are assembled by desymmetrizing cyclization of aryl/alkenyl halide-tethered malononitriles. The use of an organic reductant, (EtO)MeSiH, is crucial to the enantioselectivity and reactivity.
View Article and Find Full Text PDFAcc Chem Res
September 2021
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
Recently, alkene dicarbofunctionalization, i.e., the powerful organic synthesis method of alkene difunctionalization with two carbon sources, emerged as a formidable reaction with immense promise to synthesize complex molecules expeditiously from simple chemicals.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2021
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6, Canada.
An enantioselective consecutive cyclization/coupling process, catalyzed by palladium is reported. Stereoinduction arises from an enantioselective carbopalladation, generating an intermediate which promotes a nucleopalladation step. The dual cyclization sequence was compatible with a variety of alkyne-tethered oxygen- and nitrogen-centered nucleophiles, and a variety of alkenyl-tethered aryl iodides, to forge numerous bisheterocycles in good yields and high regio- and enantioselectivities.
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