Design and Synthesis of TY‐Phos and Application in Palladium‐Catalyzed Enantioselective Fluoroarylation ofgem‐Difluoroalkenes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(51), P. 22957 - 22962

Published: Sept. 25, 2020

Abstract The first example of highly enantioselective fluoroarylation gem‐difluoroalkenes with aryl halides is presented by using a new chiral sulfinamide phosphine ( Sadphos ) type ligand TY‐Phos . N‐Me‐ can be easily synthesized on gram scale from readily available starting materials in three steps. Salient features this work including materials, good yields, high enantioselectivities as well broad substrate scope make approach very practical and attractive. Notably, the asymmetric synthesis an analogue biologically active molecule also reported.

Language: Английский

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Catalytic and Enantioselective Control of the C–N Stereogenic Axis via the Pictet–Spengler Reaction

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(22), P. 12279 - 12283

Published: March 2, 2021

An unprecedented example of a chiral phosphoric acid-catalyzed atroposelective Pictet-Spengler reaction N-arylindoles is reported. Highly enantioenriched N-aryl-tetrahydro-β-carbolines with C-N bond axial chirality are obtained via dynamic kinetic resolution. The hydrogen donor introduced on the bottom aromatic ring, forming secondary interaction phosphoryl oxygen, essential to achieving high enantioselectivity. A wide variety substituents tolerable this transformation provide up 98 % ee. application electron-withdrawing group-substituted benzaldehydes enables control both and point stereogenicity. Biological evaluation new unique scaffold shows promising antiproliferative activity emphasizes significance synthesis.

Language: Английский

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Design and Synthesis of WJ-Phos, and Application in Cu-Catalyzed Enantioselective Boroacylation of 1,1-Disubstituted Allenes

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(8), P. 6890 - 6895

Published: June 28, 2019

The highly enantioselective copper-catalyzed three-component boroacylation of 1,1-disubstituted allenes is reported by using a class chiral ligands (WJ-Phos), delivering various functionalized organoboron compounds bearing an all-carbon stereocenter in moderate to good yields with high enantioselectivities. WJ-Phos ferrocene-derived sulfinamide phosphine ligand and can be easily synthesized gram-scale from readily available starting materials short steps. salient features this reaction include yields, enantioselectivities, synthesis, diverse synthetic transformations, the development new ligand.

Language: Английский

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Axially Chiral Biaryl Monophosphine Oxides Enabled by Palladium/WJ-Phos-Catalyzed Asymmetric Suzuki–Miyaura Cross-coupling

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(2), P. 1548 - 1554

Published: Jan. 3, 2020

A highly enantioselective palladium/WJ-Phos-catalyzed Suzuki–Miyaura coupling reaction for efficient construction of axially chiral biaryl monophosphine oxides was developed. series were obtained in good yields and with high enantioselectivities. The practicability this validated the straightforward synthesis ligand demonstrated by a 100-g-scale synthesis. Moreover, various functionalizations product make it as platform molecule other phosphines.

Language: Английский

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Recent Advances in the Development of Chiral Gold Complexes for Catalytic Asymmetric Catalysis

Chemistry - An Asian Journal, Journal Year: 2021, Volume and Issue: 16(5), P. 364 - 377

Published: Jan. 2, 2021

Asymmetric gold catalysis has been rapidly developed in the past ten years. Breakthroughs have made by rational design and meticulous selection of chiral ligands. This review summarizes newly gold-catalyzed enantioselective organic transformations recent progress ligand (since 2016), organized according to different types ligands, including bisphosphine monophosphine phosphite-derived N-heterocyclic carbene ligands for asymmetric gold(I) as well heterocyclic oxazoline gold(III) catalysis.

Language: Английский

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Asymmetric Dearomatization of Indole by Palladium/PC‐Phos‐Catalyzed Dynamic Kinetic Transformation

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(49), P. 21991 - 21996

Published: Sept. 2, 2020

Abstract A palladium‐catalyzed intermolecular dynamic kinetic asymmetric dearomatization of 3‐arylindoles with internal alkynes was developed the use achiral Xantphos and chiral sulfinamide phosphine ligand ( PC‐Phos ) as co‐ligands. This method could deliver various spiro[indene‐1,3′‐indole] compounds in good yields (up to 95 % yield) up 98 ee . The salient features transformation include readily available substrates, ease scale‐up versatile functionalization products. mechanistic experiments gave some insights on active intermediates.

Language: Английский

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Palladium/Xu-Phos-catalyzed enantioselective cascade Heck/remote C(sp2) –H alkylation reaction

Chem, Journal Year: 2022, Volume and Issue: 8(3), P. 836 - 849

Published: Jan. 18, 2022

Language: Английский

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Enantioselective C−H Functionalization Reactions under Gold Catalysis

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(20)

Published: Jan. 11, 2022

Abstract Transition metal‐catalyzed enantioselective functionalization of ubiquitous C−H bonds has proven to be promising field as it offers the construction chiral molecular complexity in a step‐ and atom‐economical manner. In recent years, gold emerged an attractive contender for catalyzing such reactions. The unique reactivities selectivities offered by catalysts have been exploited access numerous asymmetric transformations based on gold‐catalyzed processes. Herein, this review critically highlights major advances discoveries made under catalysis which is accompanied mechanistic insights at appropriate places.

Language: Английский

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Palladium/TY-Phos-Catalyzed Asymmetric Heck/Tsuji–Trost Reaction of o-Bromophenols with 1,3-Dienes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(8), P. 4378 - 4383

Published: Feb. 16, 2023

2,3-Dihydrobenzofurans are crucial building blocks in the synthesis of natural products and pharmaceutical molecules. However, their asymmetric has been a long-standing formidable challenge so far. In this work, we developed highly enantioselective Pd/TY-Phos-catalyzed Heck/Tsuji-Trost reaction o-bromophenols with various 1,3-dienes, allowing expedient access to chiral substituted 2,3-dihydrobenzofurans. This features excellent regio- enantiocontrol, high functional group tolerance, easy scalability. More importantly, demonstration method as valuable tool for construction optically pure (R)-tremetone fomannoxin is highlighted.

Language: Английский

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Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 31, 2024

ConspectusPalladium catalysis, as one of the most important strategies in asymmetric synthesis, has continuously attracted attention organic chemists. With development chiral ligands, increasingly challenging reactions and substantial progress catalysis are being realized.Since 2014, we have focused on exploiting a series sulfinamide phosphine ligands called "Sadphos," including Ming-Phos, Xu-Phos, Xiao-Phos, Xiang-Phos, TY-Phos, PC-Phos, GF-Phos, WJ-Phos. These can be easily prepared two to four steps using commercial materials. new types shown remarkable performance transition-metal-catalyzed reactions, especially Pd-catalyzed transformations. X-ray diffraction analysis, mechanistic studies, density functional theory calculations revealed that Sadphos coordinate with Pd0 PdII species Pd0/P, Pd0/P,S, or PdII/P,O modes.This Account summarizes our recent efforts toward palladium-catalyzed enantioselective ligands. were found privileged very crucial promote by increasing reactivity enantioselectivity. Ming-Phos is an effective ligand coupling intramolecular Heck providing highly trisubstituted allenes, axially anilides, gem-diarylmethine silanes, disubstituted dihydroisoquinolinones. Incorporation electron-rich cyclohexyl group moiety afforded which showed unique effect transformations, reductive Heck, dearomative Mizoroki–Heck, tandem Heck/Suzuki coupling, carboiodination, carboamination, cross-coupling reactions. Using similar strategy, synthesized more electron–rich TY-Phos Xiang-Phos bearing t-butyl 1-adamantyl at P atoms, respectively. Regarding stereoelectronic features, these characteristic best choice satisfy requirements fluoroarylation gem-difluoroalkenes, intermolecular α-arylation aldehydes, carboetherification alkenyl oximes, carboheterofunctionalization 2,3-dihydrofurans. Compared aforementioned attractive features high nucleophilicity originating from CH2PPh2 ortho-substituent side aryl ring, presumably responsible for its efficiency. The Pd/Xiao-Phos catalyst system shows good secondary oxides, affording P-stereogenic products multiple molecular skeletons. modification basic backbone introducing xanthene skeleton motivated us design synthesize monophosphines, named PC-Phos GF-Phos. various arylation sulfenate anions, denitrogenative cyclization benzotriazoles, dearomatization indoles. practicability GF-Phos was validated three-component N-tosylhydrazones, halides, terminal alkynes, well N-tosylhydrazones vinyl iodides pendent amines. In addition, ferrocene-derived WJ-Phos employed Suzuki–Miyaura reaction, biaryl monophosphine oxides excellent enantiomeric excesses.

Language: Английский

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