Vinylboron compounds are important compounds in organic chemistry and biology. In this communication, we developed a copper(I)-catalyzed, highly regio- and stereoselective radical -hydroboration of ynamides with -heterocyclic carbene (NHC)-ligated borane is reported, which leads to a series of -boryl enmides that can be conveniently transformed into various multi-substituted enamides. Further investigation showcased that our method is robust and scalable. The mechanism of this unique reaction is studied and discussed.
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http://dx.doi.org/10.1016/j.isci.2022.104977 | DOI Listing |
Org Lett
January 2025
Yunnan Key Laboratory of Modern Separation Analysis and Substance Transformation, College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, China.
A copper-catalyzed [2,3]-sigmatropic rearrangement of azide-ynamides via selenium ylides is disclosed, which leads to the practical and divergent synthesis of a variety of tricyclic heterocycles bearing a quaternary carbon stereocenter in generally moderate to excellent yields. Significantly, this method represents the first [2,3]-sigmatropic rearrangement of the selenium ylide based on alkynes and an unprecedented [2,3]-sigmatropic rearrangement via α-imino copper carbenes.
View Article and Find Full Text PDFChem Sci
October 2024
Institute of Chemistry, Casali Center of Applied Chemistry, The Hebrew University of Jerusalem Jerusalem 9190401 Israel
Spiro N-heterocycles, particularly aza-spiro piperidines, have shown significant promise in pharmaceutical applications due to their ability to enhance physicochemical properties. Despite their potential, the preparation of these complex structures poses significant challenges. To address this, we propose a one-pot dearomative spirocyclization reaction of ynamides.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, 361005, Xiamen, China.
The dehydro-Diels-Alder (DDA) reaction is a powerful method for the construction of aromatic compounds. However, the enantioselective DDA reaction has been rarely developed, probably due to the competitive thermal reaction. Herein, we report a copper-catalyzed enantioselective DDA reaction through vinyl cation pathway.
View Article and Find Full Text PDFMolecules
July 2024
Laboratoire de Chimie Moléculaire et Thio-organique (LCMT), CNRS UMR 6507, ENSICAEN, Université de Caen, Normandie Univ, 6 Bd Maréchal Juin, 14050 Caen, France.
A novel synthesis strategy to access 2-alkoxyquinoline derivatives via a palladium-driven cascade reaction is disclosed. Unlike classic methods based on the alkylation of 2-quinolones with alkyl halides, the present method benefits from the de novo assembly of the quinoline core starting from 1,3-butadiynamides. Palladium-catalyzed reaction cascades with -(2-iodophenyl)--tosyl-1,3-butadiynamides and primary alcohols as external nucleophiles proceed under mild reaction conditions and selectively deliver a variety of differently functionalized 4-alkenyl 2-alkoxyquinolines in a single batch transformation.
View Article and Find Full Text PDFBeilstein J Org Chem
March 2024
School of Chemistry, University of Birmingham, Birmingham, B15 2TT, UK.
A polysubstituted 3-aminoimidazo[5,1-]oxazol-6-ium framework has been accessed from a new nitrenoid reagent by a two-step ynamide annulation and imidazolium ring-formation sequence. Metalation with Au(I), Cu(I) and Ir(I) at the C2 position provides an L-shaped NHC ligand scaffold that has been validated in gold-catalysed alkyne hydration and arylative cyclisation reactions.
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