The first asymmetric synthesis of α,α-disubstituted allylic N-arylamines based on a palladium-catalyzed allylic amination has been developed. The protocol uses highly modular vinyl cyclic carbonates and unactivated aromatic amine nucleophiles as substrates. The catalytic process features minimal waste production, ample scope in reaction partners, high asymmetric induction up to 97% ee, and operational simplicity.
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http://dx.doi.org/10.1021/jacs.6b08841 | DOI Listing |
Org Lett
January 2025
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Chemical Biology Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, People's Republic of China.
We present a versatile palladium-catalyzed glycosylation platform that enables facile access to structurally diverse N-O-linked glycosides with constantly excellent regio- and stereoselectivities. Importantly, this approach offers a broad substrate scope, low catalyst loadings, and outstanding chemoselectivity, allowing for the selective reaction of oximes/hydroximic acids over hydroxyl groups that would otherwise pose challenges in conventional glycosylation methods. The synthetic utility of this method is further exemplified through a range of synthetic transformations and late-stage modification of bioactive molecules.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry, Indian Institute of Science Education and Research (IISER)-Pune, Dr. Homi Bhabha Road, Pashan, Pune, Maharashtra 411008, India.
A Pd (II)-catalyzed direct C3-(sp)-H alkenylation of heteroarenes using benzothiazole as a directing group was successfully achieved. A wide range of 2--alkylpyrroles undergo an oxidative coupling with a variety of acrylates to furnish highly regio- and chemoselective E-alkenylation products at the C3 position. An important intermediate complex has been isolated and characterized so as to have an insight into the mechanism.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Basic Education, Shanxi Agricultural University, Jinzhong, Shanxi 030801, P. R. China.
DFT calculations have been performed to gain insight into the mechanism of hydrocarbonylation of olefins and the origin of regio- and chemoselectivity. It is shown that the most feasible mechanism involves five steps: (i) decomposition of acetic formic anhydride, (ii) hydropalladation of olefins, (iii) CO migratory insertion, (iv) iodide-assisted acetate-formate exchange, and (v) formylation or carboxylation. Importantly, carboxylation proceeds via the decomposition of anhydride, followed by reductive elimination instead of direct hydrolysis of anhydride.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
Faculty of Life Science and Technology, Kunming, University of Science and Technology, Kunming, 650500, P. R. China.
A practical, effective, and regioselective palladium-catalyzed ring opening/[4+2] annulation of enaminones with cyclopropenones for the controllable synthesis of highly substituted γ-butenolides and γ-lactams has been described. This method for the first time reports the regio-selective annulation reaction on the carbon and amine groups of the enaminone structure. This reaction is characterized by its wide substrate scope, good functional group compatibility, moderate to good yields, scale-up synthesis, and versatile transformations, providing a versatile and general protocol to construct γ-butenolides and γ-lactams.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal Bypass Road, Bhauri, Bhopal 462066, MP, India.
We report herein a directing group-controlled, palladium-catalyzed, regio-, stereo-, and enantiospecific anti-carboxylation of unactivated, internal allenes enabled via the synergistic interplay of a rationally designed bidentate directing group, palladium catalyst, and a multifunctional acetate ligand. The corresponding trans allyl ester was obtained in excellent yields with exclusive δ-regioselectivity and anti-carboxypalladation stereocontrol. The acetate ligand of the palladium catalyst controls the regio-, stereo- and enantioselectivity in the desired transformation.
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