P(NMe₂)₃-Mediated Regioselective N-Alkylation of 2-Pyridones via Direct Deoxygenation of α-Keto Esters

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3657 - 3665

Published: Feb. 17, 2024

A practical and regioselective direct N-alkylation of 2-pyridones is enabled by use α-keto esters in the P(NMe2)3-mediated deoxygenation process. The reaction proceeds under mild conditions to produce N-alkylated with high selectivity generality, protocol shown be applicable for scale-up synthesis, which makes it promising applications.

Language: Английский

---

Sequential In Situ-Formed Kukhtin–Ramirez Adduct and P(NMe₂)₃-Catalyzed O-Phosphination of α-Dicarbonyls with P(O)–H

Organic Letters, Journal Year: 2023, Volume and Issue: 25(42), P. 7595 - 7600

Published: Oct. 13, 2023

O-Phosphination of α-dicarbonyls via sequential in situ formation a Kukhtin-Ramirez adduct and P(NMe2)3-catalyzed process has been exploited for the synthesis α-phosphoryloxy carbonyls. A range P(O)-H derivatives, including diarylphosphine oxides, arylphosphinates, phosphinates, are competent candidates to be introduced into this transformation, various carbonyls obtained. This approach possesses advantages mild conditions, simple operations, atom economy, high efficiency, gram-scale synthesis, which make it promising toolbox.

Language: Английский

---

Deoxygenative Cyclopropanation of Aldehydes with Acyl‐Stabilized Sulfur Ylides

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

Herein, we described a novel [1+1+1] deoxygenative cyclopropanation between sulfur ylides and aldehydes, which is distinctive from traditional epoxidation reactions. The method offers straightforward approach for the synthesis of highly stereoselective, functionalized, structurally diverse tertiary cyclopropyl thioethers. reaction demonstrates broad substrate scope excellent compatibility with various functional groups, rendering it particularly suitable late-stage modifications pharmaceuticals natural products, as well compounds. Additionally, β,β-disubstituted enals can also engage in reaction, instead undergoing classic through Michael addition reaction-induced cyclization ylides, thus yielding synthetically important vinylcyclopropanes chemoselectivity diastereoselectivity.

Language: Английский

---

Moderation of the Electronic Structure of Phosphamides to Execute the Catalytic Appel Reaction Bypassing Phosphine

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(21), P. 15851 - 15863

Published: Oct. 19, 2024

A set of structurally analogous, albeit electronically distinct, phosphamides (1aa-10aa) is prepared, and the effect electronic amendment due to p-substitution has been tested for conversion alcohols halides via Appel reaction. The −OMe-substituted diphosphamide (8aa) remains most active, providing ∼96% with a TON 11 in moderate reaction conditions large substrate scope. Halide formation follows pseudo-first-order rate constant (kobs) 7.13 × 10–5 s–1. Temp-dependent kinetics Eyring analyses reveal activation parameters ΔH‡ 28.95 (±1.6) kcal mol–1, ΔS‡ −70.02 (±0.4) cal K–1 ΔG‡298 49.81 (±1.2) mol–1. deuterium labeling study highlights O–H dissociation alcohol as rate-determining step, while Hammett analysis p-substituted benzyl indicates positive charge accumulation at phosphorus center during HOMO–LUMO energy NPA show that p–OMe substitutions 8aa make "P═O" bond more ionic corresponding aminophosphine nucleophilic, which are favorable In situ detection salt, [R3PX]CX3 alkoxy phosphonium cation [R3POR]X, validates pathway mediated by phosphamides.

Language: Английский

---

Pd-Catalyzed Chemodivergent Synthesis of 1-Indanones via Diethyl Zinc-Mediated Precise Switching of Umpolung Reactivity

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9706 - 9712

Published: July 10, 2023

Herein, we unveiled an efficient intramolecular umpolung chemodivergent cascade route for synthesizing 1-indanones via precisely switching the reactivity between α-diketone and π-allyl Pd complex. This successful merging of strategies is accomplished by employing a catalyst Et2Zn, which provides broad array with good yield selectivity. The salient feature involves amphiphilic behaviors both allyl functionality in two engineered mild reaction conditions. Furthermore, scale up synthesis postsynthetic transformations amplify significance current protocol. Additionally, have achieved diastereomers ether alcohol derivatives 1-indanone efficiently synthetic transformation.

Language: Английский

---

Synthesis and Characterization of Phosphate‐Catecholate Chelated Nd(III), Zr(IV), and Al(III) Complexes

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 26(30)

Published: Aug. 11, 2023

Abstract Metal phosphates are important catalysts and materials in synthesis chemistry. Herein, we describe the characterization of phosphate‐catecholate chelated Nd(III), Zr(IV) Al(III) chlorides ( 2 – 5 ). These species achieved via ethyl chloride elimination reaction oxophosphoranes with corresponding metal chlorides. The product represent a new serial monometallic bimetallic complexes stabilized by both P−O catecholate‐O donors. findings pave way for future explorations such catalysis.

Language: Английский

---

Synthesis of acyclic nucleoside analogues through P(NMe2)3-Mediated regioselective N-alkylation

Tetrahedron, Journal Year: 2024, Volume and Issue: 162, P. 134126 - 134126

Published: July 4, 2024

Language: Английский

---

Efficient Synthesis of Cyanohydrin Esters: P(NMe₂)₃ Mediated Direct Deoxygenation of Acyl Cyanides with Carboxylic Acids

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(16), P. 11777 - 11782

Published: Aug. 8, 2024

An efficient synthesis of cyanohydrin esters via a P(NMe2)3 mediated direct deoxygenation process has been exploited, circumventing the release or transformation CN─ anion during reaction. This approach possesses broad scope and acts as powerful supplement for construction diverse esters. It offers advantages such mild conditions, straightforward operations, excellent scalability, affirming feasibility versatility this highlighting its potential in practical synthesis.

Language: Английский

---

An Efficient Method for Thioesterification of Carboxylic Acid with Sulfenylchloride

Tetrahedron, Journal Year: 2024, Volume and Issue: unknown, P. 134422 - 134422

Published: Dec. 1, 2024

Language: Английский

---