Catalytic Asymmetric P–H Insertion Reactions

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 20031 - 20040

Published: Aug. 29, 2023

Albeit notable endeavors in enantioselective carbene insertion into X–H bonds (X = C, O, N, S, Si, B), the catalytic asymmetric P–H reactions still stand for a long-lasting challenge. By merging transition-metal catalysis with organocatalysis, we achieve scalable transformation between diazo pyrazoleamides and H-phosphine oxides that upon subsequent reduction delivers wide variety of optically active β-hydroxyl phosphine good yields high enantioselectivity. The achiral copper catalyst fosters carbenoid bond, while chiral cinchona alkaloid-derived organocatalyst controls outcome. Density functional theory (DFT) calculations further reveal chelates to organocatalyst, enhances its acidity, accordingly promotes proton transfer. Our work showcases potential combining organocatalysis realize elusive reactions.

Language: Английский

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Zn-Catalyzed Dehydroxylative Phosphorylation of Allylic Alcohols with P(III)-Nucleophiles

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3033 - 3048

Published: Feb. 19, 2024

A novel and efficient protocol for the synthesis of diarylallyl-functionalized phosphonates, phosphinates, phosphine oxides through zinc-catalyzed dehydroxylative phosphorylation allylic alcohols with P(III)-nucleophiles via a Michaelis–Arbuzov-type rearrangement is reported. broad range (P(OR)3, ArP(OR)2, Ar2P(OR)) are well tolerated in this reaction, expected products could be synthesized good to excellent yields under optimal reaction conditions. The can easily scaled up at gram-synthesis level. Furthermore, step-by-step control experiments, kinetic study 31P NMR tracking we acquired insights into proposed possible mechanism transformation.

Language: Английский

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Michael Addition Reaction between Dehydroalanines and Phosphites Enabled the Introduction of Phosphonates into Oligopeptides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(22), P. 4767 - 4772

Published: May 23, 2024

A method for introducing a range of phosphonates into oligopeptides through Michael addition reaction between dehydroalanine and phosphite is presented. The offers mild, cheap, straightforward approach to peptide phosphorylation that has potential applications in chemical biology medicinal chemistry. Moreover, the introduction phosphonate group short antibacterial peptides described demonstrate its utility, leading discovery phosphonated with potent broad-spectrum activity.

Language: Английский

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Comprehensive Biosafety Profile of Carbomer-Based Hydrogel Formulations Incorporating Phosphorus Derivatives

Gels, Journal Year: 2024, Volume and Issue: 10(7), P. 477 - 477

Published: July 18, 2024

Determining the safety of a newly developed experimental product is crucial condition for its medical use, especially clinical trials. In this regard, four hydrogel-type formulations were manufactured, all which based on carbomer (Blank-CP940) and encapsulated with caffeine (CAF-CP940), phosphorus derivatives (phenyl phosphinic (CAF-S1-CP940) 2-carboxyethyl phenyl acids (CAF-S2-CP940)). The main aim research was to provide comprehensive outline biosafety profile above-mentioned hydrogels. complex in vitro screening (cell viability, cytotoxicity, morphological changes response exposure, nuclei morphology) two types healthy skin cell lines (HaCaT-human keratinocytes JB6 Cl 41-5a-murine epidermal cells) exhibited good when both treated 24 h 150 μg/mL each hydrogel. A analysis hydrogel's impact genetic HaCaT cells sustains experiments. completed vivo ovo assays. outcome revealed that hydrogels exerted biocompatibility after topical application BALB/c nude mice's skin. It also lack toxicity exposure hen's chicken embryo. Further investigations are needed, regarding therapeutic efficacy long-term use potential translatability.

Language: Английский

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Visible Light-Induced Cobalt-Catalyzed 1,3-Diphosphination of Alkenes

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(18), P. 9749 - 9756

Published: Jan. 1, 2024

A novel cobalt-catalyzed radical 1,3-diphosphination of alkenes was developed, which enables straightforward access to 1,3-diphosphine skeleton compounds under mild conditions.

Language: Английский

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