Enantioselective Synthesis of Axially Chiral Alkylidenecyclobutanes via Palladium-Catalyzed N-Tosylhydrazone-Based Carbene Coupling DOI

Xiaoqin Ning,

Tonglin Zhao,

Yulei Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 11, 2025

The synthesis of axially chiral alkylidenecyclobutanes remains challenging due to the requirement both an efficient asymmetric catalytic system and preservation its inherent strained ring structure. We herein disclose enantioselective carbene cross-coupling reaction cyclobutanecarbaldehyde-derived N-tosylhydrazones with aryl bromides, enabled by palladium catalysis in combination elaborately modified sulfinamide phosphine ligand (Sadphos). This method demonstrates feasibility constructing axial chirality on a metal intermediate precisely through sequential process enantiodetermined migratory insertion followed central-to-axial-chirality-transfer β-H elimination. provides access diverse featuring heteroatom-substituted, tertiary all-carbon quaternary stereocenter excellent yields (up 95%) high enantioselectivities 95% ee). Moreover, enantiomers can be selectively obtained choosing either cis- or trans-cyclobutane substrates stereospecific manner.

Language: Английский

Copper‐Catalyzed Cyclopropenation of Alkynes with Difluoromethyl Carbene† DOI
Yong Yang, Paramasivam Sivaguru, Qingmin Song

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Comprehensive Summary The [2+1] cycloaddition of alkynes with fluoroalkyl carbenes represents the most straightforward approach for constructing fluoroalkylated cyclopropenes. However, until now, this strategy has not been applicable to difluoromethyl carbene, as its precursor, diazomethane, tends undergo [3+2] form pyrazoles. This study presents first example copper‐catalyzed cyclopropenation employing difluoroacetaldehyde triftosylhydrazone carbene precursor. A wide range internal and terminal alkynes, featuring diverse functional groups, were efficiently converted into corresponding cyclopropenes in good high yields. Mechanistic investigations, supported by DFT calculations, revealed that bulky Tp Br3 Cu(NCMe) catalyst plays a pivotal role facilitating via concerted pathway.

Language: Английский

Citations

0
Enantiodivergent dearomative single-atom skeletal editing: a magic methodology DOI
Leiyang Lv

Trends in Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 1, 2025

Language: Английский

Citations

0
A Novel Synthesis Strategy for Poly(Arylene‐Vinylene) Derivatives by Elemental Sulfur‐Mediated Polyolefination DOI Creative Commons
Peter Conen,

Florian J. O. Niedermaier,

Sophia Abou El Mirate

et al.

Macromolecular Rapid Communications, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

Herein, a new synthetic access to poly(arylene-1,2-diarylvinylene) (PAV-DA) derivatives is presented by novel polyolefination of bifunctional N-tosylhydrazones using base-activated elemental sulfur. PAV-DAs are particularly interesting due their aggregation-induced emission (AIE) properties, resulting in high solid-state photoluminescence quantum yields. The procedure allows the successful synthesis eight homopolymers and two copolymers with different arylene backbones aryl side chains from easily accessible monomers, not requiring use expensive or highly hazardous materials. polymers obtained good yields number average molecular weights up 26.9 kDa. Thermal analysis reveals exceptionally thermal stability degradation temperatures as 541 °C glass transition 263 °C. Furthermore, it found that polymer properties adjustable via copolymerization.

Language: Английский

Citations

0
Research Progress on the Reaction of Carbon Dioxide with Hydrazones and Their Derivatives DOI Creative Commons

Hongxia Sun,

Shao-Xuan Gong,

Hongyang Zhang

et al.

Molecules, Journal Year: 2025, Volume and Issue: 30(9), P. 1987 - 1987

Published: April 29, 2025

CO2, an abundant and renewable C1 source, presents significant potential for applications in organic synthesis. Hydrazones, recognized their distinctive properties, exhibit high versatility synthetic chemistry, facilitating numerous chemical transformations. Given crucial roles synthesis, the combination of CO2 with hydrazones has garnered increasing research interest. This review provides a comprehensive summary recent progress reactions involving or derivatives. These include coupling amines N-tosylhydrazones umpolung-mediated carboxylation hydrazones/N-tosylhydrazones cyclization lactamization incorporating CO2. transformations utilize diverse reactivity derivatives to capture convert generating valuable compounds both academic practical relevance. Additionally, examines mechanisms underlying these reactions, offering critical insights advancing this area.

Language: Английский

Citations

0
Iodine-mediated synthesis of indolyl-1,3,4-thiadiazole amine derivatives and their DFT analysis DOI Creative Commons

Vartika Vaishya,

Manish Kumar Mehra, Sarvesh Kumar Pandey

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(19), P. 15108 - 15115

Published: Jan. 1, 2025

This study reports a metal-free, three-component synthesis of substituted indolyl-1,3,4-thiadiazole amines, their functionalization into diverse N-heterocycles, and theoretical evaluation via DFT analysis.

Language: Английский

Citations

0
Enantioselective Synthesis of Axially Chiral Alkylidenecyclobutanes via Palladium-Catalyzed N-Tosylhydrazone-Based Carbene Coupling DOI

Xiaoqin Ning,

Tonglin Zhao,

Yulei Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 11, 2025

The synthesis of axially chiral alkylidenecyclobutanes remains challenging due to the requirement both an efficient asymmetric catalytic system and preservation its inherent strained ring structure. We herein disclose enantioselective carbene cross-coupling reaction cyclobutanecarbaldehyde-derived N-tosylhydrazones with aryl bromides, enabled by palladium catalysis in combination elaborately modified sulfinamide phosphine ligand (Sadphos). This method demonstrates feasibility constructing axial chirality on a metal intermediate precisely through sequential process enantiodetermined migratory insertion followed central-to-axial-chirality-transfer β-H elimination. provides access diverse featuring heteroatom-substituted, tertiary all-carbon quaternary stereocenter excellent yields (up 95%) high enantioselectivities 95% ee). Moreover, enantiomers can be selectively obtained choosing either cis- or trans-cyclobutane substrates stereospecific manner.

Language: Английский

Citations

0