Synthesis and characterization of new P(III) and P(V) bis(azido)phosphines/phosphoranes supported by an ,'-bis(2,6-diisopropylphenyl) imidazolin-2-iminato (IPrN) ligand and their reactivity with various secondary and tertiary phosphines result in the formation of chiral and/or asymmetric mono(phosphinimino)azidophosphines via the Staudinger reaction. The reaction of IPrNP(N) () or IPrNP(S)(N) () with an excess of tertiary phosphine resulted in the chemoselective formation of IPrNP(N)(NPMe) () or IPrNP(S)N(NPR) (), respectively. The chemoselective Staudinger reactivity was also observed in reactions using a secondary phosphine (HPCy) to produce IPrNP(S)N[NP(H)Cy] (), which exists in equilibrium with a tautomeric IPrNP(S)N[N(H)PCy] form (), as confirmed by P-P nuclear Overhauser effect spectroscopy (NOESY). Density functional theory (DFT) calculations point to a combination of energetically unfavorable lowest unoccupied molecular orbitals (LUMOs) and the accumulation of increasing negative charge at the terminal azido-nitrogen upon a single azide-to-phosphinimine conversion that gave rise to the observed chemoselectivity.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.inorgchem.4c00120 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Chemoselective Staudinger Reactivity of Bis(azido)phosphines Supported with a π-Donating Imidazolin-2-iminato Ligand.
Inorg Chem
April 2024
Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7, Canada.
Synthesis and characterization of new P(III) and P(V) bis(azido)phosphines/phosphoranes supported by an ,'-bis(2,6-diisopropylphenyl) imidazolin-2-iminato (IPrN) ligand and their reactivity with various secondary and tertiary phosphines result in the formation of chiral and/or asymmetric mono(phosphinimino)azidophosphines via the Staudinger reaction. The reaction of IPrNP(N) () or IPrNP(S)(N) () with an excess of tertiary phosphine resulted in the chemoselective formation of IPrNP(N)(NPMe) () or IPrNP(S)N(NPR) (), respectively. The chemoselective Staudinger reactivity was also observed in reactions using a secondary phosphine (HPCy) to produce IPrNP(S)N[NP(H)Cy] (), which exists in equilibrium with a tautomeric IPrNP(S)N[N(H)PCy] form (), as confirmed by P-P nuclear Overhauser effect spectroscopy (NOESY).
View Article and Find Full Text PDFBioorthogonal Conjugation-Assisted Purification Method for Profiling Cell Surface Proteome.
Anal Chem
January 2022
Department of Biomedical Sciences, College of Veterinary Medicine and Life Sciences, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon 999077, Hong Kong China.
Surface biotinylation has been widely adapted in profiling the cellular proteome associated with the plasma membrane. However, the workflow is subject to interference from the cytoplasmic biotin-associated proteins that compete for streptavidin-binding during purification. Here we established a bioorthogonal conjugation-assisted purification (BCAP) workflow that utilizes the Staudinger chemoselective ligation to label and isolate surface-associated proteins while minimizing the binding of endogenous biotin-associated proteins.
View Article and Find Full Text PDFBioorthogonal phosphines were introduced in the context of the Staudinger ligation over 20 years ago. Since that time, phosphine probes have been used in myriad applications to tag azide-functionalized biomolecules. The Staudinger ligation also paved the way for the development of other phosphorus-based chemistries, many of which are widely employed in biological experiments.
View Article and Find Full Text PDFSolid-Phase Total Synthesis of Yaku'amide B Enabled by Traceless Staudinger Ligation.
Angew Chem Int Ed Engl
March 2020
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
We report a solid-phase strategy for total synthesis of the peptidic natural product yaku'amide B (1), which exhibits antiproliferative activity against various cancer cells. Its linear tridecapeptide sequence bears four β,β-dialkylated α,β-dehydroamino acid residues and is capped with an N-terminal acyl group (NTA) and a C-terminal amine (CTA). To realize the Fmoc-based solid-phase synthesis of this complex structure, we developed new methods for enamide formation, enamide deprotection, and C-terminal modification.
View Article and Find Full Text PDFVinylphosphonites for Staudinger-induced chemoselective peptide cyclization and functionalization.
Chem Sci
July 2019
Leibniz-Forschungsinstitut für Molekulare Pharmakologie (FMP) , Chemical Biology Department , Robert-Rössle-Strasse 10 , 13125 Berlin , Germany . Email:
In this paper, we introduce vinylphosphonites for chemoselective Staudinger-phosphonite reactions (SPhR) with azides to form vinylphosphonamidates for the subsequent modification of cysteine residues in peptides and proteins. An electron-rich alkene is turned into an electron-deficient vinylphosphonamidate, thereby inducing electrophilic reactivity for a following thiol addition. We show that by varying the phosphonamidate ester substituent we can fine-tune the reactivity of the thiol addition and even control the functional properties of the final conjugate.
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!