Regioselective and Stereoselective Difluoromethylation of Enamides with Difluoromethyltriphenylphosphonium Bromide via Photoredox Catalysis.

Org Lett

Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials , Nanjing Tech University, Nanjing 211816 , China.

Published: August 2019

A regioselective and stereoselective difluoromethylation of enamides with bench-stable and easily accessible difluoromethyltriphenylphosphonium bromide is described. A broad array of synthetically important and geometrically defined β-difluoromethylated enamides bearing various functional groups are obtained with up to 91% yield.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.orglett.9b02361DOI Listing

Publication Analysis

Top Keywords

regioselective stereoselective
8
stereoselective difluoromethylation
8
difluoromethylation enamides
8
difluoromethyltriphenylphosphonium bromide
8
enamides difluoromethyltriphenylphosphonium
4
bromide photoredox
4
photoredox catalysis
4
catalysis regioselective
4
enamides bench-stable
4
bench-stable easily
4

Similar Publications

An unprecedented synergistic copper- and amine-catalyzed cyclization of enynone is reported. This reaction features an efficient and straightforward construction of multisubstituted tetralone through an amine-assisted regioselective oxygen atom transfer process and stereoselective intramolecular Michael addition cyclization. Under dehydrative reaction conditions, the synthesis of tetrahydronaphthylimine derivatives with ketone group tolerance is achieved, which could be challenging via traditional methods.

View Article and Find Full Text PDF

Aldolases are powerful C-C bond-forming enzymes for asymmetric organic synthesis because of their supreme stereoselectivity, diverse electrophiles and nucleophiles, and promising scalability. Stereodivergent engineering of aldolases to tune the selectivity for the synthesis of stereoisomers of chiral molecules is highly desirable but has rarely been reported. This study documented the semirational engineering of the decarboxylative aldolase UstD with the focused rational iterative site-specific mutagenesis (FRISM) strategy to perform a C-C bond-forming reaction with dione electrophiles.

View Article and Find Full Text PDF

Zero-Valent Copper Catalysis Enables Regio- and Stereoselective Difunctionalization of Alkynes.

Angew Chem Int Ed Engl

January 2025

Jain University - Ramanagara Campus, Centre for Nano and Material Sciences, Jakkasandra Post Kanakapura Taluk, Ramanagara-562112, Bangalore, 562112, Bangalore, INDIA.

The development of a metallic copper-based catalyst system remains a significant challenge. Herein, we report the synthesis of highly stable, active, and reusable Cu0 catalyst for the carboboration of alkynes using carbon electrophiles and bis(pinacolato)diboron (B2pin2) as chemical feedstocks to afford di- and trisubstituted vinylboronate esters in a regio- and stereoselective manner with appreciable turnover number (TON) of up to 2535 under mild reaction conditions. This three-component coupling reaction works well with a variety of substituted electrophiles and alkynes with broad functional group tolerance.

View Article and Find Full Text PDF

Enzymatic Cascades for Stereoselective and Regioselective Amide Bond Assembly.

Angew Chem Int Ed Engl

January 2025

The University of Manchester, School of Chemistry & Manchester Institute of Biotechnology, 131 Princess Street, M1 7DN, Manchester, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.

Amide bond formation is fundamental in nature and is widely used in the synthesis of pharmaceuticals and other valuable products. Current methods for amide synthesis are often step and atom inefficient, requiring the use of protecting groups, deleterious reagents and organic solvents that create significant waste. The development of cleaner and more efficient catalytic methods for amide synthesis remains an urgent unmet need.

View Article and Find Full Text PDF

Protein Engineering of Substrate Specificity toward Nitrilases: Strategies and Challenges.

J Agric Food Chem

January 2025

Key Laboratory of Carbohydrate Chemistry and Biotechnology, Ministry of Education, School of Life Sciences and Health Engineering, Jiangnan University, Wuxi 214122, PR China.

Nitrilase is extensively applied across diverse sectors owing to its unique catalytic properties. Nevertheless, in industrial production, nitrilases often face issues such as low catalytic efficiency, limited substrate range, suboptimal selectivity, and side reaction products, which have garnered heightened attention. With the widespread recognition that the structure of enzymes has a direct impact on their catalytic properties, an increasing number of researchers are beginning to optimize the functional characteristics of nitrilases by modifying their structures, in order to meet specific industrial or biotechnology application needs.

View Article and Find Full Text PDF

Want 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!