Catalytic enantioselective conjunctive cross-couplings that employ Grignard reagents are shown to furnish an array of nonracemic chiral organoboronic esters in an efficient and highly selective fashion. The utility of sodium triflate in facilitating this reaction is two-fold: it enables "ate" complex formation and overcomes catalytic inhibition by halide ions.
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http://dx.doi.org/10.1021/jacs.6b12663 | DOI Listing |
Org Lett
November 2024
School of Chemistry, University of Hyderabad, Gachibowli 500046, Telangana, India.
Allyl amines are vital components in various biologically important molecules and play a significant role in their function. Presently, most methods are geared toward the preparation of di- and trisubstituted allyl amines, leaving a gap for the development of more versatile approaches. We herein describe an approach to yield tetrasubstituted allyl amines through palladium (Pd)-catalyzed regioselective dicarbofunctionalization of masked N-phthalimide-protected propargyl amines.
View Article and Find Full Text PDFAcc Chem Res
November 2024
Department of Chemistry, Rutgers University, 73 Warren Street, Newark, New Jersey 07102, United States.
Dalton Trans
January 2024
Serveis Centrals d'Instrumentació Científica (SCIC). Universitat Jaume I, Avda. Sos Baynat s/n, 12071, Castellón, Spain.
Carboxylate-assisted Pd-catalyzed C-H bond activation constitutes a mild and versatile synthetic tool to efficiently and selectively cleave inert C-H bonds. Herein, we demonstrate a simple method to experimentally evaluate both reactivity and selectivity in such systems using mass spectrometry (MS) methods. The N-heterocyclic carbene (NHC) cations [(NHC)PdX], bearing as X ligand bases commonly used to promote the C-H activation (carboxylates and bicarbonate), are generated in the gas-phase by ESI-MS.
View Article and Find Full Text PDFAcc Chem Res
February 2022
Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, California 92037, United States.
Enolate alkylation and conjugate addition into an α,β-unsaturated system have served as long-standing strategic disconnections for the installation of α- or β-substituents on carbonyl-containing compounds. At the onset of our efforts to develop C-H activation reactions for organic synthesis, we set our eye toward developing asymmetric β-C-H activation reactions of aliphatic acids with the perspective that this bond-forming event could serve as a more flexible retrosynthetic surrogate for both canonical carbonyl-related asymmetric transformations.In this Account, we describe our early efforts using strongly coordinating chiral oxazolines to probe reaction mechanism and the stereochemical nature of the C-H cleavage transition state.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2021
School of Pharmacy, Third Military Medical University, Gao Tanyan Avenue, Chongqing, 400038, China.
A Pd-catalyzed regio- and stereoselective alkynylallylation of a specific C-C σ bond in cyclopropenes, using allyl propiolates as both allylation and alkynylation reagents, has been achieved for the first time. By merging selective C(sp )-C(sp ) bond scission with conjunctive cross-couplings, this decarboxylative reorganization reaction features fascinating atom and step economy and provides an efficient approach to highly functionalized dienynes from readily available substrates. Without further optimization, gram-scale products can be easily obtained by such a simple, neutral, and low-cost catalytic system with high TONs.
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