New methodology for difluoromethylation and difluoromethylenation of aldehydes and ketones based on nucleophilic fluorination using diethyl difluoromethylphosphonate (1) was developed.

Download full-text PDF

Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2632590PMC
http://dx.doi.org/10.1016/j.tet.2008.10.006DOI Listing

Publication Analysis

Top Keywords

difluoromethylation difluoromethylenation
8
difluoromethylenation aldehydes
8
aldehydes ketones
8
diethyl difluoromethylphosphonate
8
nucleophilic difluoromethylation
4
ketones diethyl
4
difluoromethylphosphonate methodology
4
methodology difluoromethylation
4
ketones based
4
based nucleophilic
4

Similar Publications

Herein, we report a simple and versatile difluoromethylene-imide reaction in which a series of olefins can undergo a difluoromethylenimine reaction under photocatalytic conditions through an energy transfer (EnT) process. The reaction has mild conditions and a wide range of applicability. We successfully synthesized 27 molecules containing difluoromethylene units, featuring easily accessible starting materials and operational simplicity.

View Article and Find Full Text PDF

General Defluoroalkylation of Trifluoromethylarenes with Both Electron-Donating and -Withdrawing Alkenes.

J Org Chem

September 2024

Key Laboratory for Green Organic Synthesis and Application of Hunan Province, Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, China.

The incorporation of gem-difluoromethylene units into organic molecules remains a formidable challenge. Conventional methodologies for constructing aryldifluoromethyl derivatives relied on the use of high-functional fluorinating regents under harsh conditions. Herein, we report general and efficient photoredox catalytic systems for defluoroalkylation of readily available trifluoromethylarenes through selective C-F cleavage to deliver gem-difluoromethyl radicals which proceed through reductive addition to both electron-donating and withdrawing alkenes under transition-metal free conditions.

View Article and Find Full Text PDF
Article Synopsis
  • - Fluorine-containing molecules are becoming more common in pharmaceuticals and other applications, with the cyanodifluoromethyl group being notable for its size and distinct electronic properties compared to the trifluoromethyl group.
  • - The synthesis of cyanodifluoromethyl compounds is complex, requiring multiple steps and reactive reagents, but this research introduces a copper-mediated method that simplifies the process using TMSCFCN.
  • - This new method is versatile, allowing late-stage modifications of complex molecules, and the reaction mechanism has been studied to confirm the feasibility of the process, yielding important pharmaceutical analogues.
View Article and Find Full Text PDF

A Journey of the Development of Privileged Difluorocarbene Reagents TMSCFX (X = Br, F, Cl) for Organic Synthesis.

Acc Chem Res

March 2024

Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai 200032, China.

ConspectusAs fluorine has played an increasingly important role in modulating the physical, chemical, and biological properties of organic molecules, the selective introduction of fluorine atom(s) or fluorinated moieties into target molecules has become a powerful tool in the development of new pharmaceuticals, agrochemicals, and functional materials. In this context, the difluoromethylene (CF) and difluoromethyl (CFH) groups are of special interest because of their ability to serve as bioisosteres of ethereal oxygen atoms and hydroxyl (OH) and thiol (SH) groups, respectively. Difluorocarbene is one of the most versatile reactive intermediates to incorporate CF and CFH groups; however, before 2006, most of the previously known difluorocarbene reagents suffered from several drawbacks such as using ozone-depleting substances (ODSs), difficult-to-handle reagents, or harsh reaction conditions or having narrow substrate scope and/or low yields.

View Article and Find Full Text PDF

The introduction of difluoromethylene moieties into organic molecules has garnered significant attention due to their profound influence on the physicochemical and biological properties of compounds. Nonetheless, the existing approaches for accessing difluoroalkanes from readily available feedstock chemicals remain limited. In this study, we present an efficient and modular protocol for the synthesis of difluorinated compounds from alkenes, employing the readily accessible reagent, ClCFSONa, as a versatile "difluoromethylene" linchpin.

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!