Nickel-Catalyzed Trifluoromethylselenolation of Aryl and Alkenyl-Triflates: Scope and Mechanism

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 12553 - 12562

Published: Sept. 11, 2023

The nickel-catalyzed trifluoromethylselenolation of aryl and vinyl triflates is described herein, encompassing synthesis method development an understanding the reaction. challenge lies in propensity C(sp2)–SeCF3 product to undergo oxidative addition nickel(0) intermediates, potentially initiating catalyst deactivation pathways. In this study, we disclose that Xantphos/Ni(COD)2 catalytic system efficient for trifluoromethylselenides. key elementary steps delineate cycles have been investigated by a joint experimental computational mechanistic investigation support Ni0/NiII process. Xantphos/Ni0 was found react with both ArOTf ArSeCF3 give corresponding (Xantphos)NiIIAr(X) intermediates (X = OTf or SeCF3), complex (Xantphos)NiIIAr(OTf) emerging as most stable one. line observations, studies indicate faster than but thermodynamically much less stable. Thereof, reversible shown be product. relative stability products attributed coordination mode Xantphos ligand (κ2 vs κ3) at nickel(II) intermediates. Finally, demonstrate compounds can prepared using air-stable (Xantphos)NiII precatalyst.

Language: Английский

Direct Trifluoromethylselenolation and Fluoroalkylselenolation of C−H Bonds: Recent Advances in Reagents Development and Reactions

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(38)

Published: Aug. 3, 2023

Abstract Due to their high lipophilicity and strong electron‐withdrawing property, more attention has been paid introducing trifluoromethylseleno fluoroalkylseleno moieties into organic molecules. In this short review, we categorize the synthesis of compounds that combine selenium fluorinated two main types: trifluoromethylselenolation (CF 3 Se) fluoroalkylselenolation (R f Se, except CF Se). This review aims provide a summary recent advances in direct C−H from reagents application. Based on method how R Se group was introduced, content is divided three parts: transition‐metal‐free reactions, transition‐metal‐mediated/catalyzed reactions photo‐catalyzed reactions. The general substrate scope, mechanism limitations would also be discussed so hope will serve as an inspiration for further research appealing field.

Language: Английский

Photocatalytic Perfluoroalkylation of Disulfides and Diselenides. Syntheses of Perfluoroalkyl Thio- and Seleno-ethers

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(15), P. 10867 - 10877

Published: July 22, 2024

The synthesis of alkyl(aryl)-fluoroalkyl sulfanyl [R(Ar)-S-R

Language: Английский