1.3 Synthesis of Small Fluorinated Carbocycles DOI
Lauriane C. Peyrical, André B. Charette

Published: Jan. 1, 2024

Abstract Small carbocycles, such as three- and four-membered rings, are highly strained motifs that represent an interesting class of organic compounds. Fluorinated analogs these scaffolds, combining the attractive features both small carbocycles fluorinated groups, have been studied for several decades, particularly in field medicinal chemistry. In recent years, achievements new developments reported synthesis carbocycles. particular, various substituents found increasing significance, fluoromethyl group (CFH2), difluoromethyl (CF2H), trifluoromethyl (CF3), pentafluorosulfanyl (SF5) group. Reviewed herein synthetic strategies developed between 2017 2024 to afford rings with emerging substituents.

Language: Английский

The Carbene Chemistry of N-Sulfonyl Hydrazones: The Past, Present, and Future DOI
Xiaolong Zhang, Paramasivam Sivaguru,

Yongzhen Pan

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

N-Sulfonyl hydrazones have been extensively used as operationally safe carbene precursors in modern organic synthesis due to their ready availability, facile functionalization, and environmental benignity. Over the past two decades, there has tremendous progress chemistry of N-sulfonyl presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Many transfer reactions are unique cannot be achieved by any alternative methods. The discovery novel development highly enantioselective new skeletal editing represent notable recent achievements hydrazones. This review describes overall made hydrazones, organized based on reaction types, spotlighting current state-of-the-art remaining challenges addressed future. Special emphasis is devoted identifying, describing, comparing scope limitations methodologies, key mechanistic scenarios, potential applications complex molecules.

Language: Английский

Citations

3
Dirhodium Complexes Heterochiral-at-the-Metal Centers: An Alternative Type of Paddlewheel Catalyst for Asymmetric Synthesis DOI Creative Commons
Matthias Peeters, Lorenzo Baldinelli,

Sofia Lerda

et al.

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

Published: April 4, 2025

The prototype of an entirely new class dirhodium paddlewheel complexes is disclosed, which chiral at both inequivalent metal centers although it carries just three different achiral μ-bridging equatorial ligands. One them a carboxamidate, ensures selective carbene formation the Rh[O3N] face catalyst; moreover, -NH group engages ester carbonyl emerging rhodium intermediate derived from α-stannylated α-diazoacetate in interligand hydrogen bonding, critically important for controlling stereochemical course ensuing [2 + 1] cycloaddition. heterochiral catalyst furnished stannylated cyclopropane derivatives with excellent diastereo- and enantioselectivity; quaternary trifluoromethylated stereocenter was obtained unprecedented level asymmetric induction.

Language: Английский

Citations

0
A Photocatalytic Approach to Radical 1-(Trifluoromethyl)cyclopropanation DOI Creative Commons

Sven Timmann,

Moritz T. H. Dilchert,

Jörg Dietzel

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7232 - 7240

Published: April 17, 2025

Language: Английский

Citations

0
In Situ Observation of Elusive Dirhodium Carbenes and Studies on the Innate Role of Carboxamidate Ligands in Dirhodium Paddlewheel Complexes: A Combined Experimental and Computational Approach DOI Creative Commons
Matthias Peeters, Lorenzo Baldinelli, Markus Leutzsch

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 11, 2024

Carboxamidates as equatorial ligands in dirhodium paddlewheel catalysts are widely believed to increase selectivity at the expense of reactivity. The results combined experimental and computational approach described this paper show that one has beware such generalizations. First,

Language: Английский

Citations

1
Total Synthesis of the Humulene‐Derived Sesquiterpenoid (‐)‐Integrifolian‐1,5‐dione DOI Creative Commons

Anne Zimmer,

Alois Fürstner

ChemistryEurope, Journal Year: 2024, Volume and Issue: 2(6)

Published: Oct. 10, 2024

Abstract The oxygenated sesquiterpenoid (‐)‐integrifolian‐1,5‐dione, which originates from a plant that finds widespread use in South American traditional medicine, is distinguished by rigid bicyclic framework consisting of cyclopropane cis ‐annulated to cyclodecane ring. first total synthesis this demanding target described, relies on highly selective cyclopropanation reaction an α‐stannylated‐α‐diazoester catalyzed heteroleptic dirhodium paddlewheel complex, followed unprecedented Stille‐type cross coupling the resulting stannylated with methyl iodide as electrophilic partner form all‐carbon quaternary stereocenter at one bridgehead positions. Equally decisive was bicyclization strategy based lactonization/ring expansion ultimately allowed strained ten‐membered carbocycle be forged.

Language: Английский

Citations

1
Synthesis of fluorine-containing α-alkyl-α-diazoesters and their utility in enantioselective cyclopropanation DOI
Bijaya Bagale,

Kristin M. Sobie,

Jeffrey D. Mighion

et al.

Tetrahedron Letters, Journal Year: 2024, Volume and Issue: 142, P. 155094 - 155094

Published: May 3, 2024

Language: Английский

Citations

0
1.3 Synthesis of Small Fluorinated Carbocycles DOI
Lauriane C. Peyrical, André B. Charette

Published: Jan. 1, 2024

Abstract Small carbocycles, such as three- and four-membered rings, are highly strained motifs that represent an interesting class of organic compounds. Fluorinated analogs these scaffolds, combining the attractive features both small carbocycles fluorinated groups, have been studied for several decades, particularly in field medicinal chemistry. In recent years, achievements new developments reported synthesis carbocycles. particular, various substituents found increasing significance, fluoromethyl group (CFH2), difluoromethyl (CF2H), trifluoromethyl (CF3), pentafluorosulfanyl (SF5) group. Reviewed herein synthetic strategies developed between 2017 2024 to afford rings with emerging substituents.

Language: Английский

Citations

0