Nickel‐Catalyzed Asymmetric Hydrogenation of α‐Substituted Vinylphosphonates and Diarylvinylphosphine Oxides DOI

Hanlin Wei,

Hao Chen, Jianzhong Chen

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 135(6)

Published: Dec. 12, 2022

Abstract Chiral α‐substituted ethylphosphonate and ethylphosphine oxide compounds are widely used in drugs, pesticides, ligands. However, their catalytic asymmetric synthesis is still rare. Of the only hydrogenation methods available at present, all cases use rare metal catalysts. Herein, we report an efficient earth‐abundant transition‐metal nickel catalyzed affording corresponding chiral products with up to 99 % yield, 96 ee (enantiomeric excess) (99 ee, after recrystallization) 1000 S/C (substrate/catalyst); this also first study on of terminal olefins using a catalyst under hydrogen atmosphere. The mechanism was investigated via deuterium‐labelling experiments calculations which indicate that two added atoms come from gas. Additionally, it believed reaction involves Ni II rather than 0 cyclic process based weak attractive interactions between olefin substrate.

Language: Английский

Copper‐Catalyzed Chemoselective Asymmetric Hydrogenation of C=O Bonds of Exocyclic α,β‐Unsaturated Pentanones DOI Open Access

Jing Guan,

Jianzhong Chen, Yicong Luo

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(35)

Published: June 12, 2023

Abstract A highly chemoselective earth‐abundant transition metal copper catalyzed asymmetric hydrogenation of C=O bonds exocyclic α,β‐unsaturated pentanones was realized using H 2 . The desired products were obtained with up to 99 % yield and 96 ee (enantiomeric excess) (99 ee, after recrystallization). corresponding chiral allylic pentanol can be converted into several bioactive molecules. mechanism investigated via deuterium‐labelling experiments control experiments, which indicate that the keto‐enol isomerization rate substrate is faster than also show Cu−H complex only catalyze chemoselectively reduction carbonyl group. Computational results multiple attractive dispersion interactions (MADI effect) between catalyst bulky substituents play important roles stabilize states reduce generation by‐products.

Language: Английский

Citations

2
Design and Synthesis of Spirochroman‐2‐on‐4,1'‐indan‐7'‐ol and Its Application for Synthesizing Chiral Monophosphinite Ligands† DOI

Yang‐Ming Zhang,

Shu‐Min Guo,

Q Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(22), P. 2988 - 2994

Published: June 30, 2023

Comprehensive Summary The design and synthesis of spirochroman‐2‐on‐4,1'‐indan‐7'‐ol (SCIOL) its application for synthesizing chiral monophosphinite ligands are reported. features a tandem double Friedel‐Crafts reaction/lactonization to construct the spiro framework desired racemic SCIOL was obtained via 6 steps with total yield 44.5%. Using an inclusion resolution N ‐benzylcinchonidinium chloride, optical could be in good yields on gram scale. preliminary studies indicated that corresponding exhibit high catalytic activity enantioselectivity (up 94% ee) rhodium‐catalyzed asymmetric hydrogenation ‐acetyl dehydroamino esters. These outcomes highlight significant potential as useful development ligands.

Language: Английский

Citations

1
Asymmetric Additions Empowered by OrganoCatalysts, Metal Catalysts, and Deep Natural Eutectic Solvents (NADES) DOI Creative Commons
Elisabete P. Carreiro, Gesine J. Hermann, Hans‐Jürgen Federsel

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 6631 - 6638

Published: May 2, 2024

This article is a history of an industrial-academic partnership that started almost two decades ago and details the evolution relationship between small academic research group spin-out company located in Portugal. Their activities have ranged from development new metal-based catalytic systems for asymmetric epoxidations, allylic alkylations, arylations to novel cinchona-based organocatalysts hydrosilylations Michael additions. Current common interests are centered on chiral Natural Deep Eutectic Solvent systems, which they investigating different types reaction systems.

Language: Английский

Citations

0
Application of mixed phosphorus/sulfur ligands based on terpenoids to Pd-catalyzed asymmetric allylic substitution and Rh-catalyzed hydrogenation DOI
Konstantin N. Gavrilov, Ilya V. Chuchelkin, Vladislav K. Gavrilov

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(31), P. 6362 - 6369

Published: Jan. 1, 2024

A small library of easily prepared diamidophosphite-sulfides based on 1,3-thioether alcohols, primarily terpenoid nature, was developed. Upon complexation with Pd(II) ions, these hemilabile ligands showed the ability to form both

Language: Английский

Citations

0
Cobalt‐katalysierte enantioselektive Hydrierung von dreifach substituierten carbocyclischen Olefinen: Zugang zu chiralen cyclischen Amiden DOI Creative Commons
Soumyadeep Chakrabortty,

Katharina Konieczny,

Felix J. de Zwart

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(26)

Published: Feb. 27, 2023

Abstract Die enantioselektive Hydrierung von cyclischen Enamiden wurde mit einem Cobalt‐Bisphosphin‐Katalysator erreicht. Reduktion verschiedenster dreifach substituierter carbocyclischen Enamide zu den entsprechenden gesättigten Amiden erfolgte hoher Aktivität und ausgezeichneter Enantioselektivität (bis 99 %) unter Verwendung des Systems CoCl 2 /( S , )‐Ph‐BPE. Methode lässt sich auf die Synthese chiraler Amine durch eine basische Hydrolyse der Hydrierungsprodukte ausweiten. Erste mechanistische Untersuchungen deuten Anwesenheit einer high‐spin Cobalt(II)‐Spezie im katalytischen Cyclus hin. Wir postulieren Kohlenstoff‐Kohlenstoff‐Doppelbindung über einen Sigma‐Bindungs‐Metathese‐Weg.

Citations

0
Direct and Rapid Synthesis of Arylphosphines (PIII) by Oxalyl Chloride Promoted Reduction of Inorganic Phosphorus Salts [TBA][H2PO4] with Trichlorosilane and Palladium Catalysis DOI Creative Commons
Xiaofeng Wu,

Yaling Tian,

Tao Liu

et al.

Research Square (Research Square), Journal Year: 2023, Volume and Issue: unknown

Published: July 5, 2023

Abstract Given the high demand for organophosphorus compounds (OPCs), developments of sustainable routes toward OPCs synthesis attract much attention. Numerous efforts are contributing to P 4 transformations into 1 chemistry. Nevertheless, existing methods necessitate energy-immense multisteps often utilize corrosive and dangerous reagents originating from /P red allotropes, harmful intermediates, chemical waste, impeding further exploration practical applications. Herein, direct efficient transformation inorganic phosphates [TBA][H 2 PO ] is demonstrated. These salts were activated by cost-efficient oxalyl chloride at 20°C in 5 minutes, through a double chlorination OH on phosphorus upon elimination CO molecules, followed reducing resultant intermediate with trichlorosilane, then coupling haloaryls under palladium-catalysis provide desired OPCs. Diverse tolerance various functionalities aryl halides achieved potential scale-up industrial applications, eliminating reliance extortionate, problematic allotropes. X-ray diffraction DFT calculations revealed [TBA][PO Cl ].

Language: Английский

Citations

0
Nickel‐Catalyzed Asymmetric Hydrogenation of α‐Substituted Vinylphosphonates and Diarylvinylphosphine Oxides DOI

Hanlin Wei,

Hao Chen, Jianzhong Chen

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 135(6)

Published: Dec. 12, 2022

Abstract Chiral α‐substituted ethylphosphonate and ethylphosphine oxide compounds are widely used in drugs, pesticides, ligands. However, their catalytic asymmetric synthesis is still rare. Of the only hydrogenation methods available at present, all cases use rare metal catalysts. Herein, we report an efficient earth‐abundant transition‐metal nickel catalyzed affording corresponding chiral products with up to 99 % yield, 96 ee (enantiomeric excess) (99 ee, after recrystallization) 1000 S/C (substrate/catalyst); this also first study on of terminal olefins using a catalyst under hydrogen atmosphere. The mechanism was investigated via deuterium‐labelling experiments calculations which indicate that two added atoms come from gas. Additionally, it believed reaction involves Ni II rather than 0 cyclic process based weak attractive interactions between olefin substrate.

Language: Английский

Citations

0