Rhodium‐Catalyzed Asymmetric Conjugate Addition of Organoboronic Acids to Carbonyl‐Activated Alkenyl Azaarenes DOI
Huilong Zhu, Long Yin,

Zhiqian Chang

et al.

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(15), P. 3142 - 3147

Published: March 25, 2020

Abstract The enantioselective synthesis of chiral azaarenes by rhodium‐catalyzed asymmetric conjugate addition organoboronic acids to carbonyl‐activated alkenyl was reported. Diverse were produced in up 99% yield and with ee (>60 examples). Catalytic syntheses dexchlorpheniramine dexbrompheniramine realized using the developed method. magnified image

Language: Английский

Enantioselective Hydrophosphination of Terminal Alkenyl Aza‐Heteroarenes DOI Creative Commons
Esther G. Sinnema, Tizian‐Frank Ramspoth, Reinder H. Bouma

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(7)

Published: Dec. 22, 2023

Abstract This paper presents a Mn(I)‐catalysed methodology for the enantioselective hydrophosphination of terminal alkenyl aza‐heteroarenes. The catalyst operates through H−P bond activation, enabling successful diverse range alkenyl‐heteroarenes with high enantioselectivity. presented protocol addresses inherently low reactivity and commonly encountered suboptimal enantioselectivities these challenging substrates. As an important application we show that this method facilitates synthesis non‐symmetric tridentate P,N,P‐containing ligand like structure in just two synthetic steps using single catalytic system.

Language: Английский

Citations

8
Enantioselective [3 + 2] Cycloaddition of Vinylcyclopropanes with Alkenyl N-Heteroarenes Enabled by Palladium Catalysis DOI
Wen‐Dao Chu, Yating Wang,

Tian-Tian Liang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(22), P. 3965 - 3969

Published: May 31, 2022

The first catalytic enantioselective [3 + 2] cycloaddition reaction between vinylcyclopropanes and alkenyl N-heteroarenes in the presence of LiBr a Pd(0)/SEGPHOS complex was developed. plays key role improving reactivity as mild Lewis acid.

Language: Английский

Citations

13
Catalytic Enantioselective Synthesis of Heterocyclic Vicinal Fluoroamines by Using Asymmetric Protonation: Method Development and Mechanistic Study DOI Creative Commons
Matthew W. Ashford, Chao Xu, John J. Molloy

et al.

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(53), P. 12249 - 12255

Published: June 15, 2020

Abstract A catalytic enantioselective synthesis of heterocyclic vicinal fluoroamines is reported. chiral Brønsted acid promotes aza‐Michael addition to fluoroalkenyl heterocycles give a prochiral enamine intermediate that undergoes asymmetric protonation upon rearomatization. The reaction accommodates range azaheterocycles and nucleophiles, generating the C−F stereocentre in high enantioselectivity, also amenable stereogenic C−CF 3 bonds. Extensive DFT calculations provided evidence for stereocontrolled proton transfer from catalyst substrate as rate‐determining step, showed importance steric interactions catalyst's alkyl groups enforcing enantioselectivity. Crystal structure data show dominance noncovalent core conformation, enabling modulation conformational landscape. Ramachandran‐type analysis conformer distribution Protein Data Bank mining indicated benzylic fluorination by this approach has potential improve potency several marketed drugs.

Language: Английский

Citations

20
Decarboxylative Fluorination of 2‐Pyridylacetates DOI

Ryouta Kawanishi,

Lacksany Phongphane, Seiji Iwasa

et al.

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 25(31), P. 7453 - 7456

Published: April 26, 2019

Syntheses of substituted pyridines and fluorinated compounds, which are often pharmaceutical targets, important objectives in organic chemistry. Herein, we found that decarboxylative fluorination lithium 2-pyridylacetates occur under catalyst-free conditions. The phenomenon can be applied to one-pot transformation methyl 2-pyridylacetate 2-(fluoroalkyl)pyridine by the intermediate 2-pyridylacetate. This method was also syntheses 2-(difluoroalkyl)pyridines.

Language: Английский

Citations

18
Rhodium‐Catalyzed Asymmetric Conjugate Addition of Organoboronic Acids to Carbonyl‐Activated Alkenyl Azaarenes DOI
Huilong Zhu, Long Yin,

Zhiqian Chang

et al.

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(15), P. 3142 - 3147

Published: March 25, 2020

Abstract The enantioselective synthesis of chiral azaarenes by rhodium‐catalyzed asymmetric conjugate addition organoboronic acids to carbonyl‐activated alkenyl was reported. Diverse were produced in up 99% yield and with ee (>60 examples). Catalytic syntheses dexchlorpheniramine dexbrompheniramine realized using the developed method. magnified image

Language: Английский

Citations

18