Enantioselective Cobalt(III)‐Catalyzed C−H Activation Enabled by Chiral Carboxylic Acid Cooperation

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(47), P. 15425 - 15429

Published: Oct. 6, 2018

The enantioselective cobalt(III)-catalyzed C-H alkylation was achieved through the design of a novel chiral acid. activation characterized by high position-, regio- and enantio-control under exceedingly mild reaction conditions. Thereby, robust cooperative cobalt(III) catalysis proved tolerant valuable electrophilic functional groups, including hydroxyl, bromo, iodo substituents. Mechanistic studies revealed considerable additive effect on kinetics negative non-linear-effect.

Language: Английский

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Enantioselective Cu-Catalyzed Arylation of Secondary Phosphine Oxides with Diaryliodonium Salts toward the Synthesis of P-Chiral Phosphines

Journal of the American Chemical Society, Journal Year: 2016, Volume and Issue: 138(40), P. 13183 - 13186

Published: Sept. 30, 2016

Catalytic synthesis of nonracemic P-chiral phosphine derivatives remains a significant challenge. Here we report Cu-catalyzed enantioselective arylation secondary oxides with diaryliodonium salts for the tertiary high enantiomeric excess. The new process is demonstrated on wide range substrates and leads to products that are well-established catalysts ligands.

Language: Английский

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A Planar‐Chiral Rhodium(III) Catalyst with a Sterically Demanding Cyclopentadienyl Ligand and Its Application in the Enantioselective Synthesis of Dihydroisoquinolones

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(26), P. 7714 - 7718

Published: April 6, 2018

Abstract The rapid development of enantioselective C−H activation reactions has created a demand for new types catalysts. Herein, we report the synthesis novel planar‐chiral rhodium catalyst [(C 5 H 2 t Bu CH Bu)RhI ] in two steps from commercially available [(cod)RhCl] and tert ‐butylacetylene. Pure enantiomers were obtained through separation its diastereomeric adducts with natural ( S )‐proline. promoted aryl hydroxamic acids strained alkenes to give dihydroisoquinolones high yields (up 97 %) good stereoselectivity 95 % ee ).

Language: Английский

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Enantioselective Synthesis of Chiral‐at‐Sulfur 1,2‐Benzothiazines by Cp^xRh^III‐Catalyzed C−H Functionalization of Sulfoximines

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(47), P. 15539 - 15543

Published: Oct. 10, 2018

Abstract Sulfoximines with stereogenic sulfur atoms are attractive structural motifs in drug discovery. A direct catalytic enantioselective method for the synthesis of sulfur‐chiral 1,2‐benzothiazines from readily accessible diaryl sulfoximines is presented. Rhodium(III) complexes equipped chiral cyclopentadienyl ligands and paired suitable carboxylic acid additives engage an enantiodetermining C−H activation directed by sulfoximine group. Subsequent trapping rhodacycle a broad range diazoketones gives access to S‐chiral synthetically highly substitution patterns good yields enantioselectivities.

Language: Английский

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Cooperative Effects between Chiral Cp^x–Iridium(III) Catalysts and Chiral Carboxylic Acids in Enantioselective C−H Amidations of Phosphine Oxides

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(47), P. 15088 - 15092

Published: Sept. 22, 2017

Abstract An enantioselective C−H amidation of phosphine oxides by using an iridium(III) catalyst bearing atropchiral cyclopentadienyl (Cp x ) ligand is reported. A very strong cooperative effect between the chiral Cp and a phthaloyl tert‐leucine enabled transformation. Matched–mismatched cases different acid enantiomers are shown. The amidated P‐chiral arylphosphine formed in yields up to 95 % with excellent enantioselectivities 99:1 er. Enantiospecific reduction provides access valuable phosphorus(III) compounds.

Language: Английский

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Catalytic synthesis of chiral organoheteroatom compounds of silicon, phosphorus, and sulfur via asymmetric transition metal-catalyzed C–H functionalization

Coordination Chemistry Reviews, Journal Year: 2016, Volume and Issue: 330, P. 37 - 52

Published: Sept. 21, 2016

Language: Английский

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Cp*Co(III)/MPAA-Catalyzed Enantioselective Amidation of Ferrocenes Directed by Thioamides under Mild Conditions

Organic Letters, Journal Year: 2019, Volume and Issue: 21(6), P. 1895 - 1899

Published: March 6, 2019

Cp*Cobalt(III)-catalyzed enantioselective C-H amidation of ferrocenes using monoprotected amino acids (MPAAs) as chiral ligands was developed. The reaction performed under mild conditions in high yields (up to 97%) with moderate enantioselectivity 77.5:22.5 er), providing a promising strategy create planar chirality via base-metal-catalyzed activation.

Language: Английский

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P-Chiral Phosphines Enabled by Palladium/Xiao-Phos-Catalyzed Asymmetric P–C Cross-Coupling of Secondary Phosphine Oxides and Aryl Bromides

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(51), P. 20556 - 20564

Published: Dec. 2, 2019

The development of transition-metal-catalyzed methods for the synthesis P-chiral phosphine derivatives poses a considerable challenge. Herein, we present direct Pd/Xiao-Phos-catalyzed cross-coupling reaction easily accessible secondary oxides and aryl bromides, which provides rapid access to oxides. proceeds efficiently with wide array partners deliver various tertiary in up 96% yield 97% ee. Moreover, DiPAMP ligand its analogues was also realized, demonstrates suitable pathway switching branched chain DiPAMP.

Language: Английский

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Generation of Heteroatom Stereocenters by Enantioselective C–H Functionalization

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(10), P. 9164 - 9177

Published: Aug. 30, 2019

C–H functionalization has been established as an efficient way to generate molecular complexity. The formation of stereogenic carbon atoms by asymmetric seen tremendous progress over the past decade. More recently, direct catalytic modification bonds powerfully applied noncarbon centers, which constitute a key design element biologically active molecules and chiral ligands for catalysis. This area was opened seminal report describing enantioselective silicon stereocenter. It rapidly expanded with advances in phosphorus(V) centers. Moreover, routes sulfur oxidation states IV (sulfoxides) VI (sulfoximines) have disclosed. Herein, we discuss methods using selective remote heteroatom center via inner-sphere activation mechanism.

Language: Английский

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Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Language: Английский

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