Synthesis, Journal Year: 2023, Volume and Issue: 56(14), P. 2234 - 2238
Published: Dec. 27, 2023
Abstract A practical and short synthesis of FDA approved drug, Rotigotine, is achieved in two steps from 5-methoxy-2-tetralone, which turn was synthesised by [4+2] cycloaddition the situ generated methoxyaryne its precursor aryl triflate with benzyloxybutadiene or 4-methoxyindanone via ring expansion using trimethylsilyldiazomethane.
Language: Английский
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 29, 2025
Due to their strong aromaticity and difficulties in chemo-, regio-, enantioselectivity control, asymmetric hydrogenation of naphthol derivatives 1,2,3,4-tetrahydronaphthols has remained a long-standing challenge. Herein, we report the first example homogeneous catalyzed by tethered rhodium-diamine catalysts, affording wide array optically pure high yields with excellent enantioselectivities (up 98% yield >99% ee). Mechanistic studies experimental computational approaches reveal that fluorinated solvent 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) plays vital roles control reactivity selectivity, 1-naphthol is reduced via cascade reaction pathway, including dearomative tautomerization, 1,4-hydride addition, 1,2-hydride addition sequence. A novel synergistic activation mode was proposed which HFIP assists both hydrogen molecule presence base, situ-generated fleeting keto tautomer immediately trapped Rh(III)-H species before it escapes from cage. This protocol provides straightforward practical pathway for synthesis key intermediates several chiral drugs. Particularly, Nadolol, drug treatment hypertension, angina pectoris, congestive heart failure, certain arrhythmias, enantioselectively synthesized time.
Language: Английский
Citations
1
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)
Published: Aug. 23, 2023
An iridium-catalyzed remote site-switchable hydroarylation of alkenes was reported, delivering the products functionalized at subterminal methylene and terminal methyl positions on an alkyl chain controlled by two different ligands, respectively, in good yields with to excellent site-selectivities. The catalytic system showed functional group tolerance a broad substrate scope, including unactivated activated alkenes. More importantly, regioconvergent transformations mixtures isomeric were also successfully realized. results mechanistic studies demonstrate that reaction undergoes chain-walking process give [Ar-Ir-H] complex alkene. subsequent processes proceed through modified Chalk-Harrod-type mechanism via migratory insertion alkene into Ir-C bond followed C-H reductive elimination afford hydrofunctionalization site-selectively.
Language: Английский
Citations
14
Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(13), P. 6735 - 6778
Published: Jan. 1, 2024
The review summarizes the increasing applications of chiral bisphosphine ligand Ph-BPE in catalytic asymmetric reactions past twenty years.
Language: Английский
Citations
6
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: June 28, 2024
Abstract Transition metal-catalyzed asymmetric hydrogenation is one of the most efficient methods for preparation chiral α-substituted propionic acids. However, research on this method, employing cleaner earth-abundant metal catalysts, still insufficient in both academic and industrial contexts. Herein, we report an nickel-catalyzed acrylic acids affording corresponding with up to 99.4% ee (enantiomeric excess) 10,000 S/C (substrate/catalyst). In particular, method can be used obtain ( R )-dihydroartemisinic acid 99.8:0.2 dr (diastereomeric ratio) 5000 S/C, which essential intermediate antimalarial drug Artemisinin. The reaction mechanism has been investigated via experiments DFT (Density Functional Theory) calculations, indicate that protonolysis C-Ni bond key intramolecular proton transfer from carboxylic group substrate, rate-determining step.
Language: Английский
Citations
6
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(10)
Published: Nov. 28, 2023
Asymmetric hydrogenation finds widespread application in academia and industry. And indeed, a number of processes have been implemented for the production pharma agro intermediates as well flavors & fragrances. Although these are all based on use late transition metals catalysts, there is an increasing interest base metal catalysis view their lower cost expected different substrate scope. Catalysts cobalt already shown potential enantioselective chemistry. This review outlines impressive progress made recent years cobalt-catalyzed asymmetric unsaturated substrates. We also illustrate ligand dependent specificity mechanistic variability detail. may guide further catalyst development this research area.
Language: Английский
Citations
13
JACS Au, Journal Year: 2023, Volume and Issue: 3(11), P. 2981 - 2986
Published: Oct. 20, 2023
Based on an amino-group-assisted coordination strategy and a proton-shuttle-activated outer-sphere mode, the cobalt-catalyzed asymmetric hydrogenation of α-primary amino ketones has been developed, resulting in efficient synthesis chiral vicinal alcohols bearing functionalized aryl rings high yields enantioselectivities (up to 99% enantiomeric excess (ee)) within 0.5 h.
Language: Английский
Citations
12
ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 15682 - 15690
Published: Nov. 21, 2023
The enantioselective reduction of enamides is an efficient and atom-economical way to construct chiral amine motifs. In contrast transition-metal complex based asymmetric hydrogenation, alternative biocatalytic more sustainable but remains unexploited. challenge lies in the redox potential mismatch between ground-state enzymes abiotic enamide substrates. Herein, we report a photoenzymatic strategy, expanding reaction repertoires biocatalysts previously elusive for synthesis enantioenriched amines (with up 99:1 enantiomeric ratio). Mechanistic wet experiments computational studies revealed that direct visible-light excitation hydroquinone state flavin cofactor enhances reducing capacity ene-reductases, thereby triggering single-electron process. Mild green conditions as well broad functional group tolerance make this unnatural protocol practical complement traditional chemocatalytic approaches.
Language: Английский
Citations
10
Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(4), P. 937 - 948
Published: March 21, 2024
Significant emphasis has been placed on the development of nonprecious metal alternatives to precious-metal-catalyzed reactions due lower cost and greater sustainability they can achieve. This review is part a series describing advances in nonprecious-metal-catalyzed transformations published between March June 2023 that are relevant pharmaceutical process chemistry.
Language: Английский
Citations
3
Organic Letters, Journal Year: 2023, Volume and Issue: 26(4), P. 769 - 774
Published: Dec. 4, 2023
An efficient cobalt-catalyzed asymmetric reductive amination of ketones with hydrazides has been realized, directly producing valuable chiral hydrazines in high yields and enantioselectivities (up to 98% enantiomeric excess).
Language: Английский
Citations
5
Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(41)
Published: Aug. 23, 2023
Abstract An iridium‐catalyzed remote site‐switchable hydroarylation of alkenes was reported, delivering the products functionalized at subterminal methylene and terminal methyl positions on an alkyl chain controlled by two different ligands, respectively, in good yields with to excellent site‐selectivities. The catalytic system showed functional group tolerance a broad substrate scope, including unactivated activated alkenes. More importantly, regioconvergent transformations mixtures isomeric were also successfully realized. results mechanistic studies demonstrate that reaction undergoes chain‐walking process give [Ar−Ir−H] complex alkene. subsequent processes proceed through modified Chalk–Harrod‐type mechanism via migratory insertion alkene into Ir−C bond followed C−H reductive elimination afford hydrofunctionalization site‐selectively.
Language: Английский
Citations
4