An original multi-cooperative catalytic approach was developed by combining metal-ligand cooperation and Lewis acid activation. The [(SCS)Pd] complex featuring a non-innocent indenediide-based ligand was found to be a very efficient and versatile catalyst for the Conia-ene reaction, when associated with Mg(OTf). The reaction operates at low catalytic loadings under mild conditions with HFIP as a co-solvent. It works with a variety of substrates, including those bearing internal alkynes. It displays complete 5- 6- regio-selectivity. In addition, except for the highly congested Bu-substituent, the reaction occurs with high stereo-selectivity, making it synthetically useful and complementary to known catalysts.
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http://dx.doi.org/10.1039/d0sc05036a | DOI Listing |
Org Lett
September 2024
School of Chemistry, Xi'an Key Laboratory of Sustainable Energy Material Chemistry, and MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Xi'an Jiaotong University, Xi'an 710049, China.
Chemistry
October 2024
State Key Laboratory of Antiviral Drugs, Pingyuan Laboratory, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Henan Normal University, Xinxiang, Henan, 453007, China.
Despite the existence of three competing reactions for propargyloxyoxindoles, we report a chemoselectivity switch between enantioselective propargyl [2,3]-Wittig rearrangement and Conia-ene-type reactions, with suppression of the [1,2]-Wittig-type rearrangement. Using C-symmetric imidazolidine-pyrroloimidazolone pyridine as the ligand and Ni(acac) as the Lewis acid, diverse 3-hydroxy 3-substituted oxindoles containing allenyl groups were obtained in up to 98 % yield and 99 % ee via asymmetric propargyl [2,3]-Wittig rearrangement. In the presence of AgOTf-Duanphos, chiral spiro dihydrofuran oxindoles were given in up to 98 % yield and 91 % ee through a Conia-ene-type reaction.
View Article and Find Full Text PDFChem Commun (Camb)
April 2024
Department of Organic Synthesis and Process Chemistry, CSIR-Indian Institute of Chemical Technology, Hyderabad 500007, India.
A novel one-pot protocol that enables sequential execution of an aza-Piancatelli rearrangement and a Conia-ene type reaction has been developed under Lewis acid catalysis. Here, a combination of B(CF) and Cu(OTf), triethylamine, and triphenylphosphine yielded a wide range of -fused cyclopentenone-pyrrolidine scaffolds in one pot with good yields and diastereoselectivity.
View Article and Find Full Text PDFJ Am Chem Soc
February 2024
State Key Laboratory of Chemical Oncogenomics and Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055, China.
The total syntheses of penicibilaenes A and B are described. The key step is the BuOK/DMSO-mediated tandem 5-- Conia-ene type reaction and 6-- Conia-ene type reaction to install the tricyclic [6.3.
View Article and Find Full Text PDFOrg Biomol Chem
November 2023
School of Life Science and Technology, Tokyo Institute of Technology, 4259 Nagatsuta-cho Midori-ku, Yokohama, 226-8503, Japan.
The bridged diazatricycloundecane sp-rich scaffold was synthesised the gold(I)-catalysed Conia-ene reaction. The electron-donating property of the siloxymethyl group on alkyne 1 enabled 6- cyclization, whereas the ethoxy carbonyl group on alkyne 4 led to 5- cyclization with complete regioselectivity in the Conia-ene reaction. The resulting bridged diazatricycloundecane scaffold 5 allowed the construction of a library of sp-rich compounds.
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