An effective and practical CuI-catalyzed methodology toward N-alkyl or N-methyl phosphonamides and phosphinamides was herein demonstrated. The transformation took place readily under the oxidative conditions, and plenty of N-alkylated (methylated) amides (30 examples) were successfully furnished in high efficiency (up to 92% yields). Dicumyl peroxide was considered to act either as the oxidant for the alkylation reaction or as methyl donator for the methylation protocol.
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http://dx.doi.org/10.1021/acs.joc.7b01527 | DOI Listing |
Org Lett
December 2022
Anhui Academy of Science and Technology, Anhui 232002, China.
We have developed a dual copper/photoredox-catalyzed approach for the construction of the P(O)-N bond from commercially available aromatic amines and P(O)-H compounds. This metallaphotoredox method avoids toxic or corrosive reagents and does not require prefunctionalized substrates. The reaction has a broad substrate scope and is suitable for the synthesis of phosphonamides and phosphinamides, thus complementing the previous nonphotochemical approaches.
View Article and Find Full Text PDFOrg Lett
August 2020
Institute of Chemistry and BioMedical Sciences, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
We report a redox-neutral P(O)-N coupling reaction of P(O)-H compounds with azides via photoredox and copper catalysis, providing new access to useful phosphinamides, phosphonamides, and phosphoramides. This transformation tolerates a wide range of nucleophilic functionalities including alcohol and amine nucleophiles, which makes up for the deficiency of classical nitrogen nucleophilic substitution reactions. As a demonstration of the broad potential applications of this new methodology, late-stage functionalization of a diverse array of azido-bearing natural products and drug molecules, a preliminary asymmetric reaction, and a continuous visible-light photoflow process have been developed.
View Article and Find Full Text PDFJ Org Chem
September 2017
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. China.
An effective and practical CuI-catalyzed methodology toward N-alkyl or N-methyl phosphonamides and phosphinamides was herein demonstrated. The transformation took place readily under the oxidative conditions, and plenty of N-alkylated (methylated) amides (30 examples) were successfully furnished in high efficiency (up to 92% yields). Dicumyl peroxide was considered to act either as the oxidant for the alkylation reaction or as methyl donator for the methylation protocol.
View Article and Find Full Text PDFChem Commun (Camb)
October 2013
Department of Chemistry, Kangwon National University, Chuncheon 200-701, Republic of Korea.
Rhodium-catalyzed oxidative coupling reactions via C-H activation and annulation directed by phosphonamide and phosphinamide groups were developed under aerobic conditions, which produced benzazaphosphole 1-oxides and phosphaisoquinolin-1-oxides.
View Article and Find Full Text PDFBioorg Med Chem
December 2003
Medicinal Chemistry Research, LEO Pharma, Industriparken 55, DK-2750 Ballerup, Denmark.
The design, synthesis, and structure-activity relationship (SAR) of a series of novel nonpeptidic cyclic phosphon- and phosphinamide-based hydroxamic acids as inhibitors of matrix metalloproteinases MMP-1, MMP-3, and MMP-9 are presented. Based on modelling studies and X-ray analysis, a model of the binding mode of these novel compounds in the MMP active site was obtained. This model provided a rational explanation for the observed SAR data, which included a systematic study of different S1' directed substituents, zinc-complexing groups, chirality, and variation of the cyclic phosphon- and phosphinamide rings.
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