An efficient and general method for the preparation of achiral and chiral phosphonium salts is reported. This synthesis is based on the quaternization of phosphines and their derivatives with arynes generated in situ from 2-(trimethylsilyl)aryl triflates. This methodology is successfully applied to the synthesis of new valuable P-stereogenic phosphonium triflates.
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Catalysis of an S2 pathway by geometric preorganization.
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Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA.
Bimolecular nucleophilic substitution (S2) mechanisms occupy a central place in the historical development and teaching of the field of organic chemistry. Despite the importance of S2 pathways in synthesis, catalytic control of ionic S2 pathways is rare and notably uncommon even in biocatalysis, reflecting the fact that any electrostatic interaction between a catalyst and the reacting ion pair necessarily stabilizes its charge and, by extension, reduces polar reactivity. Nucleophilic halogenase enzymes navigate this tradeoff by desolvating and positioning the halide nucleophile precisely on the S2 trajectory, using geometric preorganization to compensate for the attenuation of nucleophilicity.
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Department of Applied Chemistry, Anhui Province Engineering Laboratory for Green Pesticide Development and Application, and Anhui Province Key Laboratory of Crop Integrated Pest Management, Anhui Agricultural University, Hefei 230036, China.
Chiral P,N-ligands are of great interest and importance in the fields of metal-catalyzed enantioselective transformations and have found numerous applications spanning drug and polymer synthesis. Here, modular assembly of diverse P-stereogenic and axially chiral phosphinooxazoles ligands is achieved through palladium-catalyzed asymmetric cleavage of C-P bond/intermolecular C-H bond functionalization in high atroposelectivities and diastereoselectivities of up to >99% ee and >25:1 dr. This protocol features broad substrate scope and provides an avenue for facile construction of new P-stereogenic and axially chiral phosphinooxazoles ligands directly from the phosphonium salts and benzoxazoles/benzothiazoles.
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Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
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View Article and Find Full Text PDFDiastereoselective synthesis of bulky, strongly nucleophilic, and configurationally stable P-stereogenic tricyclic phosphines.
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Université de Toulouse, UPS, LHFA, 118 route de Narbonne, F-31062 Toulouse, France.
A very simple, one-step highly diastereoselective synthesis of bulky, configurationally and air-stable P-chiral tricyclic phosphines 3, showing an exceptionally strong nucleophilic character, has been developed. This method involves the reaction of the stable phosphonium sila-ylide 1 with aryl- and alkyl-substituted acetylene derivatives. Starting from commercially available chiral (R,S)-(+)-endo-2-norborneol, the corresponding enantiomerically pure phosphines were obtained with excellent enantioselectivities (ee ≥ 99%) and high chemical yields.
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Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB), UMR CNRS 5260, 9 Avenue Alain Savary, BP 47870, 21078 Dijon cedex, France.
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