A general method has been developed for the previously challenging arylation of cyclopropylamine and N-arylcyclopropylamines. Highly active, air-stable, and commercially available R-allylpalladium precatalysts provide access to a wide range of (hetero)arylated cyclopropylanilines in high yields. Precatalysts [(tBuBrettPhos)Pd(allyl)]OTf and [(BrettPhos)Pd(crotyl)]OTf, deliver monoarylated products, while (PtBu3)Pd(crotyl)Cl is suited for preparing unsymmetrical diarylated products. The developed conditions tolerate a range of functional groups and heterocycles, allowing access to an array of arylated cyclopropylamines, a motif present in prominent drug molecules.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.6b00377 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Ligand-Controlled C2- or C3-Selectivity Switching in the Palladium-Catalyzed C-H Arylation of Nonsubstituted 1-Pyrrole.
Org Lett
January 2025
School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan.
The C2- or C3-selective direct C-H arylation of nonsubstituted 1-pyrrole with aryl chlorides/nonaflates was achieved using catalysts derived from palladium and appropriate phosphine ligands. The site selectivity of the arylation can be switched by changing the ligands, and the C3-selective arylation of nonsubstituted 1-pyrrole was realized for the first time. BuOLi played an important role in suppressing N-arylation and accelerating C2- or C3-arylation.
View Article and Find Full Text PDFPalladium-catalyzed -arylation of (hetero)aryl chlorides with pyrroles and their analogues.
Org Biomol Chem
January 2025
School of Chemistry and Chemical Engineering, Guangxi Colleges and Universities Key Laboratory of Applied Chemistry Technology and Resource Development, Guangxi University, Nanning 530004, Guangxi, P. R. China.
We present a mild and efficient method for the arylation of N-H heteroarenes using a low-loading Pd/keYPhos catalyst (0.8 mol%). This approach employs inexpensive and structurally diverse aryl chlorides as electrophiles in reactions with indoles, pyrroles, and carbazole, enabling the construction of a wide range of -arylated products.
View Article and Find Full Text PDFSolvent-Controlled Enantiodivergent Construction of P(V)-Stereogenic Molecules via Palladium-Catalyzed Annulation of Prochiral N-Aryl Phosphonamides with Aromatic Iodides.
Angew Chem Int Ed Engl
October 2024
Xiamen Key Laboratory of Optoelectronic Materials and Advanced Manufacturing, College of Materials Science and Engineering, Huaqiao University, Xiamen, 361021, China.
In this work, we describe an efficient and modular method for enantiodivergent accessing P(V)-stereogenic molecules by utilizing the catalytic atroposelective Catellani-type C-H arylation/desymmetric intramolecular N-arylation cascade reaction. The enantioselectivity of this protocol was proved to be tuned by the polarity of the solvent, thus providing a wide range of both chiral P(V)-stereogenic enantiomers in moderate to good yields with good to excellent enantiomeric excesses. Noteworthy is that the strategy developed herein represents an unprecedented example of solvent-dictated inversion of the enantioselectivity of P(V)-stereogenic compounds.
View Article and Find Full Text PDFCatalytic Asymmetric Synthesis of Atropisomers Featuring an Aza Axis.
Acc Chem Res
September 2023
College of Chemistry and Chemical Engineering, Qingdao University, Qingdao 266071, China.
ConspectusAtropisomers bearing a rotation-restricted axis are common structural units in natural products, chiral ligands, and drugs; thus, the prevalence of asymmetric synthesis has increased in recent decades. Research into atropisomers featuring an N-containing axis (N-X atropisomers) remains in its infancy compared with the well-developed C-C atropisomer analogue. Notably, N-X atropisomers could offer divergent scaffolds, which are extremely important in bioactive molecules.
View Article and Find Full Text PDFReductive Arylation of Nitroarenes with Chloroarenes: Reducing Conditions Enable New Reactivity from Palladium Catalysts.
J Am Chem Soc
July 2023
Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.
Palladium-catalyzed C-N bond forming reactions are a key tool in modern synthetic organic chemistry. Despite advances in catalyst design enabling the use of a variety of aryl (pseudo)halides, the necessary aniline coupling partner is often synthesized in a discrete reduction step from a nitroarene. An ideal synthetic sequence would avoid the necessity of this step while maintaining the reliable reactivity of palladium catalysis.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!