Unsymmetrical phosphites react efficiently in a Staudinger reaction with p-azido-phenylalanine, which can be applied for the biotinylation of proteins, thereby expanding the scope of the chemoselective Staudinger-phosphite reaction of aryl azides with symmetrical phosphites to the corresponding phosphoramidates.
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http://dx.doi.org/10.1039/b926818a | DOI Listing |
J Org Chem
February 2024
Department of Basic Medicinal Sciences, Graduate School of Pharmaceutical Sciences, Nagoya University, Nagoya 464-8601, Japan.
Unsymmetrical -phosphonates were synthesized by a rapid (<15 s) and mild (20 °C) process in a microflow reactor as the first example of the sequential direct substitution of the chlorine atoms in PCl with alkoxyl/aryloxy groups using equivalent amounts of PCl and alcohols. The optimal base concentration differed in each step, presumably attributed to differences in the Brønsted basicity of the electrophilic intermediates. Phosphite hydrolysis was observed, and the structure-hydrolysis relationship was quantitatively evaluated.
View Article and Find Full Text PDFOrg Lett
October 2023
Key Laboratory of Natural Medicine and Immune Engineering, School of Pharmacy, Henan University, Kaifeng 475004, People's Republic of China.
Novel regioselective hydrodeoxygenation of α-diketones with phosphites as the deoxygenation reagent was realized via visible-light photoredox catalysis. Broad substrate scope and high functional group compatibility were obtained. Unsymmetric α-diketones were selectively reduced at the carbonyls of higher electrophilicity.
View Article and Find Full Text PDFOrg Lett
July 2023
Natural Product and Medicinal Chemistry Division, CSIR-Indian Institute of Integrative Medicine, Jammu 180001, India.
Herein, we present the BF/BF mediated activation of diphenyl phosphite for the formation of thionium ions from aldehydes and thiophenols. These reactive species subsequently undergo reaction with generated phenol, resulting in the synthesis of diarylmethyl thioethers. It was demonstrated that the addition of external phenol in the reaction produced unsymmetrical -diarylmethyl thioethers in good yields.
View Article and Find Full Text PDFJ Org Chem
October 2021
Natural Product and Medicinal Chemistry Division, CSIR-Indian Institute of Integrative Medicine, Jammu 180001, India.
By facilitating the chemical conversion of thiols to thiosulfonates, phosphoramidite/phosphite bearing sp-hybridized carbon serves as an ideal coupling material to forge new connections at room temperature. In this work, a functional group-induced, additive-free, novel, S-P bond-forming approach is presented. This protocol exhibits good functional group tolerance with wide applications that include phosphorylation of cysteine derivatives, development of a one-pot approach to mixed unsymmetrical thiophosphonates, and extension of the concept to different Se-P bonds.
View Article and Find Full Text PDFJ Org Chem
March 2020
Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, Denmark.
The promotion of mixed-valence interactions between redox-active, π-conjugated scaffolds is of interest when developing new conducting or electrochromic materials as well as in the construction of redox-controlled supramolecular assemblies. In this work, dimeric structures of the redox-active indenofluorene-extended tetrathiafulvalene (IF-TTF) unit were synthesized in a stepwise protocol. The synthesis relied on the development of a new unsymmetrical IF-TTF building block by a combination of phosphite-mediated and Horner-Wadsworth-Emmons reactions for introduction of the dithiafulvene units.
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