Diruthenium Tetracarboxylate-Catalyzed Enantioselective Cyclopropanation with Aryldiazoacetates DOI Creative Commons

Joshua K. Sailer,

Jack C. Sharland,

John Bacsa

et al.

Organometallics, Journal Year: 2023, Volume and Issue: 42(15), P. 2122 - 2133

Published: June 30, 2023

A series of chiral bowl-shaped diruthenium(II,III) tetracarboxylate catalysts were prepared and evaluated in asymmetric cyclopropanations with donor/acceptor carbenes derived from aryldiazoacetates. The diruthenium self-assembled to generate C4-symmetric structures an analogous manner their dirhodium counterparts. optimum catalyst was found be Ru2(S-TPPTTL)4·BArF [S-TPPTTL = (S)-2-(1,3-dioxo-4,5,6,7-tetraphenylisoindolin-2-yl)-3,3-dimethylbutanoate, BArF tetrakis(3,5-bis(trifluoromethyl)phenyl)borate], which resulted the cyclopropanation a range substrates up 94% ee. Synthesis evaluation first-row transition-metal congeners [Cu(II/II) Co(II/II)] invariably that afforded little no induction. Computational studies indicate carbene complexes these dicopper dicobalt complexes, unlike systems, are prone loss carboxylate ligands, would destroy structure critical for

Language: Английский

Catalytic Diastereo‐ and Enantioselective Cyclopropanation of gem‐Dihaloalkanes and Terminal Olefins DOI

Hou‐Lu Liu,

Xinyu Wang, Ke Gao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: May 11, 2023

Chiral cyclopropane derivatives are essential in synthetic chemistry and drug discovery. Their synthesis commonly relies on asymmetric cyclopropanation of diazo compounds, potentially explosive needing stabilizing substituents. Thus, catalytic transformations non-stabilized carbenes or carbenoids remain a formidable challenge. Herein, we report the unprecedented chromium-catalyzed readily available gem-dihaloalkanes terminal olefins. Distinct from previous approaches, serve as suitable precursors for carbenoids, furnishing various functionalized chiral cyclopropanes. Mechanistic studies, including radical trapping, non-linear effect, UV/Vis spectroscopy, provide insights into process, featuring radical-polar crossover.

Language: Английский

Citations

16
UV Light Is No Longer Required for the Photoactivation of 1,3,4-Oxadiazolines DOI Creative Commons
K Orłowska, João V. Santiago, Piotr Krajewski

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(3), P. 1964 - 1973

Published: Jan. 20, 2023

Carbenes play a key role in plethora of organic transformations. Although stabilized diazo carbonyl compounds predominate as source electrophilic carbenes, the hazardous nature nonstabilized analogues calls for their situ generation from stable precursors. Among these, 1,3,4-oxadiazolines serve diazoalkane surrogates under UV light irradiation. In view high stability, diverse reactivities, and straightforward synthesis, milder methodologies activation these that permit use UV-light-sensitive substrates are highly valued. Herein, we report visible-light-induced oxadiazolines by triplet energy transfer catalysis that, contrast to UV-induced processes, alters reactivity enables carbenes. The formed reactive species react with electron-poor olefins, thereby giving valuable spirocyclopropanes. Mechanistic investigations, both theoretical experimental, uncover plausible pathways highlight importance steps.

Language: Английский

Citations

15
Catalytic Olefin Cyclopropanation with In Situ-Generated Dialkyl Diazomethanes via Co(II)-Based Metalloradical Catalysis DOI
Bao‐Gui Cai, Claire Empel, Sripati Jana

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(17), P. 11851 - 11856

Published: Aug. 23, 2023

The synthesis of dialkyl-substituted cyclopropanes is an important challenge in with applications drug discovery and agrochemistry. Herein, we report on the gem-dialkyl situ-generated dialkyl diazo compounds under Bamford–Stevens conditions. A simple cobalt catalyst was identified to be optimal achieve high yields. Experimental computational studies suggest participation a metalloradical reaction mechanism that facilitates carbene transfer reactions provides access single step.

Language: Английский

Citations

15
Copper-Mediated Cyclization of Terminal Alkynes with CF3-Imidoyl Sulfoxonium Ylides To Construct 5-Trifluoromethylpyrroles DOI
Magdy I. El‐Zahar, Zhou Li,

Yixin Tong

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2249 - 2254

Published: March 7, 2024

A copper-mediated [3 + 2] cyclization of CF3-imidoyl sulfoxonium ylides and terminal alkynes has been demonstrated. This work provides a practical approach for assembling 5-trifluoromethylpyrroles with the merits broad substrate scope, good functional tolerance, mild reaction conditions. Control experiments DFT studies indicate that this may involve addition π-bonds by copper-carbene radicals hydrogen migration.

Language: Английский

Citations

6
Asymmetric radical cyclopropanation of alkenes DOI
Wan‐Chen Cindy Lee, X. Peter Zhang

Trends in Chemistry, Journal Year: 2022, Volume and Issue: 4(9), P. 850 - 851

Published: July 5, 2022

Language: Английский

Citations

21
Recent Advances in the Enantioselective Radical Reactions DOI Creative Commons
Tomasz Bauer, Yusuf Zaim Hakim, Paulina Morawska

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(17), P. 6252 - 6252

Published: Aug. 25, 2023

The review covers research published since 2017 and is focused on enantioselective synthesis using radical reactions. It describes recent approaches to the asymmetric of chiral molecules based application metal catalysis, dual organocatalysis finally, pure including enzyme catalysis. This focuses synthetic aspects methodology tries show which compounds can be obtained in enantiomerically enriched forms.

Language: Английский

Citations

11
Design and Synthesis of C4‐Symmetric Axially Chiral β‐Aryl Porphyrins and Application for Supporting Ir(III)‐Catalyzed Enantioselective C−H Alkylation DOI

Shanshan Yuan,

Jun‐Chao Sun,

Xiaoming Zhao

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)

Published: April 29, 2024

A hitherto unknown class of C

Language: Английский

Citations

4
CoH-catalyzed asymmetric remote hydroalkylation of heterocyclic alkenes: a rapid approach to chiral five-membered S- and O-heterocycles DOI Creative Commons
Lingzi Zhao,

Feipeng Liu,

Yan Zhuang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(23), P. 8888 - 8895

Published: Jan. 1, 2024

A highly efficient method achieves precise construction of alkyl chiral centers at remote C3-positions in five-membered S/O-heterocycles via cobalt-catalyzed asymmetric hydroalkylation heterocyclic alkenes.

Language: Английский

Citations

4
The Cascade Reaction Chemistry of Diazo Compounds with Intentionally Designed Alkene to Access Esterified Heterocycles DOI

Shi-Cui Fang,

Shao-Qun Cai,

Panpan Li

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Exploration of the cascade reactivity diazo compounds with alkenes is a challenging and largely unmet goal. Herein, we disclose light-mediated de novo synthesis esterified heterocycles under mild conditions. The reaction displays broad functional group tolerance, including wide variety alkenes, compounds, some bioactive molecules. Importantly, synthetic appeal was demonstrated for synthesizing indoleamine 2,3-dioxygenase inhibitor analogue, deethylated derivative natural product leucomidine C, anti-inflammatory agent AN669.

Language: Английский

Citations

0
Too Persistent to Resist: Aromaticity in 16e Osmapentalene Radicals Survives Regardless of Redox DOI Creative Commons
Shijie Pan, Jun Yan, Weitang Li

et al.

Chemistry, Journal Year: 2025, Volume and Issue: 7(1), P. 22 - 22

Published: Feb. 8, 2025

As one of the most important concepts in organic chemistry, aromaticity has attracted considerable attention from both theoretical and experimental chemists. Limited by traditional rules (Hückel’s Baird’s rules), species can only achieve a single state (S0 or T1) cases. In 2018, our group first reported 16 electron osmapentalene that showed S0 T1 states, which is defined as adaptive aromaticity. recent years, although aromatic compounds have been expanded, aromatics containing metal-centered radical not reported. Here, we carry out density functional theory calculations to explore corresponding radicals based on osmapentalyne osmapentalenes their states. It found exhibit regardless formed oxidation reduction, supported series indices including ΔBL, NICS, AICD, EDDB, ELF. contrast, for nonaromatic antiaromatic compound state, its cationic shows Furthermore, spin localization metal center key factor

Language: Английский

Citations

0