The Suzuki-Miyaura reaction after the Nobel prize

Coordination Chemistry Reviews, Год журнала: 2019, Номер 385, С. 137 - 173

Опубликована: Фев. 13, 2019

Язык: Английский

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A dual light-driven palladium catalyst: Breaking the barriers in carbonylation reactions

Science, Год журнала: 2020, Номер 368(6488), С. 318 - 323

Опубликована: Апрель 16, 2020

Lighting the way coming and going Catalysts accelerate chemical reactions by breaking existing bonds then forming new ones. Often, factors that favor first process can muddle second one, constraining a catalyst's generality. Torres et al. found visible light excitation of palladium complex facilitate both making carbon-halogen (see Perspective Kathe Fleischer). The reaction specifically forms acid chlorides carbonylation wide variety alkyl or aryl bromides iodides. These products in turn react further to form amides esters. Science , this issue p. 318 ; see also 242

Язык: Английский

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Functional Group Transposition: A Palladium-Catalyzed Metathesis of Ar–X σ-Bonds and Acid Chloride Synthesis

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(32), С. 10140 - 10144

Опубликована: Авг. 6, 2018

We describe the development of a new method to use palladium catalysis form functionalized aromatics: via metathesis covalent σ-bonds between Ar–X fragments. This transformation demonstrates dynamic nature palladium-based oxidative addition/reductive elimination and offers straightforward approach incorporate reactive functional groups into aryl halides through exchange reactions. The reaction has been exploited assemble acid chlorides without high energy halogenating or toxic reagents and, instead, iodides with other chlorides.

Язык: Английский

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A Type of Structurally Adaptable Aromatic Spiroketal Based Chiral Diphosphine Ligands in Asymmetric Catalysis

Accounts of Chemical Research, Год журнала: 2021, Номер 54(3), С. 668 - 684

Опубликована: Янв. 14, 2021

ConspectusWhile spectacular successes have been achieved in homogeneous catalysis with the use of achiral diphosphine ligands featuring a wide natural bite angle, such as XantPhos, chiral diphosphines that can induce large P–M–P angle their transition metal complexes are conspicuously less explored asymmetric catalysis, probably due to challenges identification and efficient construction suitable backbone. In past decade, highly synthesis aromatic spiroketals corresponding (SKPs) has developed this group.Based on one-pot catalytic tandem double hydrogenation–spiroketalization ring-closure reaction sequence, these SKP an extraordinarily long P···P distance flexible backbone readily prepared scale. Remarkably versatile coordination modes found some catalysis-relevant metals, for example, Pd, Cu, Au, Rh. Whereas enforces unusually [Pd(SKP)Cl2] [Cu(SKP)Cl] (160.1° 132.8°, respectively), it also allows bimetallic Au–Au interaction (3.254 Å) complex [Au2(SKP)Cl2] or square-planar geometry [Rh(SKP)(cod)]SbF6 complex. Such adaptable nature profound consequences demonstrated by unique performance several types reactions. One most exciting examples is SKP/Pd-catalyzed allylic amination Morita–Baylis–Hillman (MBH) adducts, which SKP/Pd excellent control regio- enantioselectivities exhibited exceptionally high efficiency (with TON up 4750) catalysis. diversity successful applications Cu-, Au-, Rh-catalyzed reactions, further attesting utilities Overall, class accessible spiroketal skeleton structures variety provided outstanding difficult transformations. The works delineated herein would be expected stimulate research efforts application type ligand provide useful clues design new angles catalyzed

Язык: Английский

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Heteroleptic copper complexes with nitrogen and phosphorus ligands in photocatalysis: Overview and perspectives

Chem Catalysis, Год журнала: 2021, Номер 1(2), С. 298 - 338

Опубликована: Июнь 14, 2021

Язык: Английский

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SPSiPs, a Class of Diphosphine Ligands Based on SPSiOL with a Large Dihedral Angle

Organic Letters, Год журнала: 2023, Номер 25(21), С. 3859 - 3863

Опубликована: Май 22, 2023

The development and the synthetic applications of a novel class diphosphine ligands (SPSiPs) based on chiral spirosilabiindane diol (SPSiOL) are presented. Starting from SPSiOL, could be readily prepared in three steps with high efficiency. This features rigid configuration, large dihedral angle, P-M-P long P-P distance. potentials SPSiPs asymmetric catalysis have also been preliminarily disclosed.

Язык: Английский

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Cation−π Interactions in the Benzylic Arylation of Toluenes with Bimetallic Catalysts

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(39), С. 12415 - 12423

Опубликована: Сен. 5, 2018

A method to directly arylate toluene derivatives with aryl bromides generate diarylmethanes, which are important building blocks in drug discovery, is described. In this method, KN(SiMe3)2 combination a (NIXANTPHOS)Pd catalyst accomplished the deprotonative activation of permit cross-coupling bromides. Good excellent yields obtained range electron-rich neutral Both and electron-poor well tolerated, even 2-chlorotoluene performs well, providing platform for introduction additional functionalization. This discovery hinges on use main group metal activate deprotonation by means cation−π interaction, secured bimetallic K(NIXANTPHOS)Pd assembly. Mechanistic computational studies support acidification K+–cation– π may prove pertinent development other, new reaction systems.

Язык: Английский

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Copper‐Catalyzed Carbonylative Hydroamidation of Styrenes to Branched Amides

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(50), С. 22441 - 22445

Опубликована: Авг. 25, 2020

Amides are one of the most ubiquitous functional groups in synthetic and medicinal chemistry. Novel rapid synthesis amides remains high demand. In this communication, a general efficient procedure for branch-selective hydroamidation vinylarenes with hydroxyamine derivatives enabled by copper catalysis has been developed first time. The reaction proceeds under mild conditions tolerates broad range groups. Applying chiral phosphine ligand, an enantioselective variant transformation was achieved, affording variety α-amides excellent enantioselectivities (up to 99 % ee) yields.

Язык: Английский

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Stereoselective Synthesis of Highly Substituted Conjugated Dienes via Pd‐Catalyzed Carbonylation of 1,3‐Diynes

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(31), С. 10683 - 10687

Опубликована: Май 24, 2019

Abstract The stereoselective synthesis of conjugated dienes was realized for the first time via Pd‐catalyzed alkoxycarbonylation easily available 1,3‐diynes. Key to success is utilization specific ligand 1,1′‐ferrocenediyl‐bis(tert‐butyl(pyridin‐2‐yl)phosphine) ( L1 ), which allows this novel transformation proceed at room temperature. A range 1,2,3,4‐tetrasubstituted are obtained in straightforward access high yields and selectivities. synthetic utility protocol showcased concise several important intermediates construction natural products rac‐cagayanin, rac‐galbulin, rac‐agastinol, cannabisin G.

Язык: Английский

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Tailored Palladium Catalysts for Selective Synthesis of Conjugated Enynes by Monocarbonylation of 1,3‐Diynes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(23), С. 9032 - 9040

Опубликована: Фев. 13, 2020

For the first time, monoalkoxycarbonylation of easily available 1,3-diynes to give synthetically useful conjugated enynes has been realized. Key success was design and utilization new ligand 2,2'-bis(tert-butyl(pyridin-2-yl)phosphanyl)-1,1'-binaphthalene (Neolephos), which permits palladium-catalyzed selective carbonylation under mild conditions, providing a general preparation functionalized 1,3-enynes in good-to-high yields with excellent chemoselectivities. Synthetic applications that showcase possibilities this novel methodology include an efficient one-pot synthesis 4-aryl-4H-pyrans as well rapid construction various heterocyclic, bicyclic, polycyclic compounds.

Язык: Английский

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