Catalytic asymmetric synthesis of spirooxindoles: recent developments

Chemical Communications, Год журнала: 2018, Номер 54(50), С. 6607 - 6621

Опубликована: Янв. 1, 2018

The past four years have witnessed significant developments in the field of catalytic asymmetric synthesis spirooxindoles, and this feature article outlines recent progress area, including contributions our group. This is divided into sections according to size type generated spiro-ring fused at C3-position oxindole core.

Язык: Английский

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Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

Chemical Reviews, Год журнала: 2018, Номер 118(16), С. 7586 - 7656

Опубликована: Июль 26, 2018

The metal-catalyzed asymmetric conjugate addition (ACA) reaction has emerged as a general and powerful approach for the construction of optically active compounds is among most significant useful reactions in synthetic organic chemistry. In recent years, great progress been made this area with use various chiral metal complexes based on different ligands. This review provides comprehensive critical information enantioselective 1,4-conjugate nonorganometallic (soft) nucleophiles their importance applications. literature covered from last 10 number examples before 2007 are included background information. divided into multiple parts according to type nucleophile involved (such C-, B-, O-, N-, S-, P-, Si-centered nucleophiles) catalyst systems used.

Язык: Английский

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Chiral Amino Acids‐Derived Catalysts and Ligands

Chinese Journal of Chemistry, Год журнала: 2018, Номер 36(9), С. 791 - 797

Опубликована: Май 23, 2018

Abstract Transforming amino acids into novel catalysts and ligands is a remarkable subset of new catalyst development in order to imitate enzymatic efficiencies. Their ability perform variety asymmetric catalytic reactions complimented by their ready availability, rich transformations, stability easy procedure. Herein, we focused on describing our endeavor developing from primary secondary acids. It includes C 2 ‐symmetric N , N' ‐dioxides, guanidine‐amides, bispidine‐based diamines, other organic salts. The account covered brief introduction about discovery, representative applications related mechanisms.

Язык: Английский

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Asymmetric Catalytic Reactions of Donor–Acceptor Cyclopropanes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(17), С. 9192 - 9204

Опубликована: Июль 28, 2020

Due to the synergistic "push-pull" effect of vicinal electron-donating and electron-withdrawing groups, donor-acceptor (D-A) cyclopropanes have been recognized as one most powerful building blocks generate polyfunctional reactive intermediates after a strain-driven ring cleavage. Enantioselective reactions D-A provide an efficient approach enantioenriched acyclic cyclic compounds. A number chiral Lewis/Brønsted acids, transition metals, organocatalysts designed for such transformations, including ring-openings, annulations, rearrangements. This minireview highlights developments new advances in this field describes synthetic opportunities offered by these interesting methodologies.

Язык: Английский

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Asymmetric Catalytic Rearrangements with α-Diazocarbonyl Compounds

Accounts of Chemical Research, Год журнала: 2022, Номер 55(3), С. 415 - 428

Опубликована: Янв. 14, 2022

Conspectusα-Diazocarbonyl compounds serve as nucleophiles, dipoles, carbene precursors, and rare electrophiles, enabling a vast array of organic transformations under the influence metal catalysts. Among them, rearrangement processes are attractive provide straightforward efficient accesses to one-carbon extension adducts or heteroatom-containing molecules. The reactions occur upon release dinitrogen after nucleophilic addition before ylide formation. Although significant progress has been made for these two types reactions, issue enantiocontrol is challenging because final optically enriched products generated via multistep inherent spacial arrangement intermediates more less on regio- enantioselectivity.In this Account, we collected several rearrangements α-diazocarbonyl compounds, showcasing catalysts tailored strategies tackling enantioselective varieties reactions. Our research group initiated catalytic asymmetric during development chiral Feng N,N′-dioxide–metal complex others. As kind useful Lewis acid catalyst complexes favorable activation various carbonyl accelerating diastereo- α-diazoesters sequential in either an intermolecular intramolecular manner. Aldehydes, acyclic cyclic ketone derivatives, α,β-unsaturated ketones could participate homologation obvious ligand-acceleration effect observed processes. For example, Roskamp–Feng reaction aldehydes gives active β-ketoesters through H-shift, overwhelming aryl shift oxygen attack. preference derivatives be excellent control An unusual electrophilic α-amination aryl/alkyl even complicated homologation/dyotropic rearrangement/interconversion/[3 + 2] cycloaddition cascade used construct dimeric polycyclic were discovered result selection ligands additives. On basis understanding interaction functional with catalysis key enantio-determining issues ylide-based rearrangements, designed new by introducing pyrazole-1-carboxyl acceptor unit, which benefit formation both carbenoid species catalyst-bound ylides deliver stereoselectivity. Taking advantage Ni(II) Co(II) N,N′-dioxide ligands, realized kinds [2,3]-sigmatropic such Doyle–Kirmse allylic sulfides selenides, [2,3]-Stevens vinyl-substituted α-diazo pyrazoleamides thioacetates, Sommelet–Hauser aryl-substituted thioamides, thio-Claisen 2-thio-indoles well. Moreover, strategy was shown applicable highly γ-selective insertion into N–H bonds secondary amines pyrazoleamides.

Язык: Английский

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Stereodivergent total synthesis of rocaglaol initiated by synergistic dual-metal-catalyzed asymmetric allylation of benzofuran-3(2H)-one

Chem, Год журнала: 2022, Номер 8(7), С. 2011 - 2022

Опубликована: Май 2, 2022

Язык: Английский

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Asymmetric Three-Component Radical Alkene Carboazidation by Direct Activation of Aliphatic C–H Bonds

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(19), С. 13347 - 13355

Опубликована: Май 6, 2024

Azide compounds are widely present in natural products and drug molecules, their easy-to-transform characteristics make them used the field of organic synthesis. The merging transition-metal catalysis with radical chemistry offers a versatile platform for carboazidation alkenes, allowing rapid assembly highly functionalized azides. However, direct use readily available hydrocarbon feedstocks as sp

Язык: Английский

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Stereodivergent assembly of tetrahydro-γ-carbolines via synergistic catalytic asymmetric cascade reaction

Nature Communications, Год журнала: 2019, Номер 10(1)

Опубликована: Дек. 5, 2019

Abstract Enantiomerically enriched indole-containing heterocycles play a vital role in bioscience, medicine, and chemistry. As one of the most attractive subtypes indole alkaloids, highly substituted tetrahydro-γ-carbolines are basic structural unit many natural products pharmaceuticals. However, syntheses with high functionalities from readily available reagents significant challenging. In particular, stereodivergent containing multi-stereogenic centers remain quite difficult. Herein, we report an expedient assembly remarkably levels stereoselective control efficient cascade process aldimine esters indolyl allylic carbonates via synergistic Cu/Ir catalyst system. Control experiments-guided optimization catalysts mechanistic investigations reveal that allylation reaction subsequent iso -Pictet-Spengler cyclization key elements to success.

Язык: Английский

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Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle–Kirmse Reaction of α-Diazo Pyrazoleamides

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(9), С. 3299 - 3305

Опубликована: Фев. 14, 2018

Although high enantioselectivity of [2,3]-sigmatropic rearrangement sulfonium ylides (Doyle–Kirmse reaction) has proven surprisingly elusive using classic chiral Rh(II) and Cu(I) catalysts, in principle it is due to the difficulty fine discrimination heterotopic lone pairs sulfur chirality inversion at ylides. Here, we show that synergistic merger new α-diazo pyrazoleamides a N,N′-dioxide-nickel(II) complex catalyst enables highly enantioselective Doyle–Kirmse reaction. The pyrazoleamide substituent serves as both an activating directing group for ready formation metal-carbene- Lewis-acid-bonded ylide intermediate assistance dual-tasking nickel(II) complex. An alternative pathway greatly improves product enantiopurity even reaction symmetric diallylsulfane. majority transformations over series aryl- or vinyl-substituted pyrazoleamindes sulfides proceed rapidly (within 5–20 min most cases) with excellent results (up 99% yield 96% ee), providing breakthrough

Язык: Английский

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Asymmetric Catalytic [2,3] Stevens and Sommelet–Hauser Rearrangements of α‐Diazo Pyrazoleamides with Sulfides

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(38), С. 13492 - 13498

Опубликована: Июль 23, 2019

Abstract Catalytic enantioselective [2,3] Stevens and Sommelet–Hauser rearrangements of α‐diazo pyrazoleamides with sulfides were achieved by utilizing chiral N , ′‐dioxide/nickel( II ) complex catalysts. These proceeded well under mild reaction conditions, providing rapid facile access to a series functionalized 1,6‐dicarbonyls or sulfane‐substituted phenylacetates high excellent enantioselectivities. The catalytic system shows stereocontrol, discriminating between the heterotopic lone pairs sulfur controlling both 1,3‐proton transfer [2,3]‐σ rearrangement.

Язык: Английский

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