Synthesis of Cyclopropenols Enabled by Visible‐Light‐Induced Organocatalyzed [2+1] Cyclization

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(10)

Опубликована: Янв. 7, 2022

Although the synthesis of common cyclopropenes has been well studied, access to cyclopropenols is rather limited. Herein, we report first α-trifluoromethylated via 2+1 cycloaddition reactions between alkynes and trifluoroacylsilanes, enabled by visible-light-induced organocatalysis. The novel ambiphilic donor-acceptor carbenes derived from trifluoroacetylsilanes reacted efficiently with both activated non-activated alkynes. reaction features simple operation, mild conditions, broad substrate scope good functional group tolerance. synthetic potential highlighted gram-scale cyclopropanols through combination cyclization high diastereoselective hydrogenation in one pot.

Язык: Английский

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Nickel‐Catalyzed Asymmetric Hydroaryloxy‐ and Hydroalkoxycarbonylation of Cyclopropenes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Июль 15, 2022

Abstract The asymmetric Reppe carbonylation reactions provide a straightforward access to α ‐chiral carbonyl compounds. reported paradigms predominantly adopted precious palladium as the catalyst. Here we report nickel‐catalyzed of cyclopropenes with phenyl formate and CO/ROH, respectively. This asymmetrical synthetic protocol features high atom economy, good functional group tolerance, which rapidly constructs polysubstituted cyclopropanecarboxylic derivatives excellent diastereo‐ enantioselectivity. utility is demonstrated by facile conversion chiral products into bioactive molecules such (−)‐Tranylcypromine (−)‐Lemborexant.

Язык: Английский

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Nickel‐Hydride‐Catalyzed Diastereo‐ and Enantioselective Hydroalkylation of Cyclopropenes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(46)

Опубликована: Сен. 20, 2022

Abstract Cyclopropanes are structural motifs that widely present in natural products and bioactive molecules, they also tremendously useful building blocks synthetic organic chemistry. Asymmetric synthesis of cyclopropane derivatives has been an intensively researched area over the years, but efficient asymmetric preparation alkylcyclopropane scaffolds remains a challenging topic. Herein, we report nickel‐hydride‐catalyzed enantioselective diastereoselective hydroalkylation cyclopropenes for facile chiral motifs. The reported method is versatile, taking place under mild reaction conditions, having broad applicability excellent functional group tolerance.

Язык: Английский

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Enantioselective Hydroalkoxylation of 1,3-Dienes via Ni-Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(7), С. 3909 - 3914

Опубликована: Фев. 10, 2023

As an advance in hydrofunctionalization, we herein report that alcohols add to 1,3-dienes with high regio- and enantioselectivity. Using Ni-DuPhos, access enantioenriched allylic ethers. Through the choice of solvent-free conditions, control reversibility C–O bond formation. This work showcases a rare example methanol as reagent asymmetric synthesis.

Язык: Английский

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Copper‐Phosphido Catalysis: Enantioselective Addition of Phosphines to Cyclopropenes**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)

Опубликована: Июнь 19, 2023

We describe a copper catalyst that promotes the addition of phosphines to cyclopropenes at ambient temperature. A range cyclopropylphosphines bearing different steric and electronic properties can now be accessed in high yields enantioselectivities. Enrichment phosphorus stereocenters is also demonstrated via Dynamic Kinetic Asymmetric Transformation (DyKAT) process. combined experimental theoretical mechanistic study supports an elementary step featuring insertion Cu

Язык: Английский

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Copper(I)‐Catalyzed Asymmetric Hydrophosphination of 3,3‐Disubstituted Cyclopropenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)

Опубликована: Авг. 18, 2023

Herein, a copper(I)-catalyzed asymmetric hydrophosphination of 3,3-disubstituted cyclopropenes is reported. It provides series phosphine derivatives in high to excellent diastereo- and enantioselectivities. The methodology enjoys broad substrate scope on both diarylphosphines. stereoselectivity attributed the stability Cu(I)-(R,R)-QUINOXP* complex presence stoichiometric HPPh2 produced phosphines, high-performance induction complex. Finally, method used for synthesis new chiral phosphine-olefin compounds built cyclopropane skeleton, one which serves as wonderful ligand Rh-catalyzed conjugate addition phenylboronic acid various α,β-unsaturated compounds.

Язык: Английский

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Desymmetrization–Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 18892 - 18898

Опубликована: Июль 5, 2024

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated synthesis series chiral functionalized cyclopropanes with high yield, enantioselectivity, diastereoselectivity (44 examples, up 93% yield >99% ee). A possible mechanism involving cyclopropene desymmetrization Co-H species imine addition Co-alkyl was proposed. study provides novel route important extends frontier metallaphotoredox

Язык: Английский

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Rh-catalyzed double carbonylation of cyclopropenes toward valerolactone derivatives via cleavage of carbon–carbon double bonds

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 25, 2025

Язык: Английский

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Asymmetric Auto‐Tandem Palladium Catalysis for 2,4‐Dienyl Carbonates: Ligand‐Controlled Divergent Synthesis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(17)

Опубликована: Фев. 14, 2022

Developing new asymmetric auto-tandem catalysis processes, especially in a divergent manner, is highly attractive but extremely challenging. Presented herein palladium-catalyzed reaction between 2,4-dienyl carbonates and o-TsNH arylimines or trifluoroacetophenones that proceeds through consecutive N-allylation, vinylogous addition, π-σ-π isomerization, another N-allylation sequence. Importantly, switchable diastereodivergent synthesis could be achieved by tuning the chiral bisphosphine ligands, which led to construction of broad spectrum fused tetrahydroquinoline architectures with moderate excellent enantioselectivity. Ligand control even enabled effective access regiodivergent azetidine chemodivergent β-H elimination fair enantioselectivity, further showing versatility current catalysis.

Язык: Английский

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Enantioselective Selenol-ene Using Rh-Hydride Catalysis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(40), С. 18246 - 18250

Опубликована: Сен. 26, 2022

This study showcases the first enantioselective hydroselenation of styrenes. Organoselenium building blocks are accessed with selectivity for branched isomer. Through a Rh-hydride pathway, C–Se bonds can be forged excellent regio- and enantiocontrol.

Язык: Английский

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