Chiral Spirocyclic Phosphoric Acids and Their Growing Applications

Chinese Journal of Chemistry, Год журнала: 2020, Номер 39(4), С. 802 - 824

Опубликована: Окт. 14, 2020

Chiral spirocyclic phosphoric acids (SPAs) are introduced in 2010 and have been versatile catalysts capable of promoting a wide range asymmetric organocatalytic reactions, such as multi-component Friedel–Crafts Pictet–Spengler Fischer indolizations, cycloaddition desymmetrization dearomatization conjugate addition reactions rearrangement etc. Moreover, diverse applications metal-organic cooperative catalysis, organic photoredox total synthesis, materials science molecular recognition beautifully illustrated. This account summarizes the past decade's advances this field highlights selected but not comprehensive significant achievements. What is most favorite original chemistry developed your research group? Developing SPINOL-phosphoric (SPAs), TM-SPINOL-phosphoric (SPAs 2.0) PCP-derived planar chiral (PPAs) for catalysis. important personality scientific research? Curiosity, optimism, self-confidence persistence. What's hobbies? book(s)? I enjoy cooking. My book Journey to West. Who influences you mostly life? mother. journal(s)? The journals publishing systematic work synthetic chemistry. Could please give us some advices on improving Chinese Journal Chemistry? Fast review, fast publication, promotion via new media.

Язык: Английский

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An overview of the applications of chiral phosphoric acid organocatalysts in enantioselective additions to CO and CN bonds

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(22), С. 6331 - 6399

Опубликована: Янв. 1, 2022

Since 2004, chiral phosphoric acids (CPAs) have emerged as highyl efficient organocatalysts, providing excellent results in a wide reaction scope. In this review, the applications of CPA for enantioselective additions to CO and CN bonds are covered.

Язык: Английский

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Asymmetric aza‐Friedel–Crafts Reaction of Cyclic Ketimines with 5‐Aminopyrazole Derivatives: Expedient Access to Pyrazole‐Based C2‐quaternary Indolin‐3‐Ones

Chemistry - A European Journal, Год журнала: 2023, Номер 29(20)

Опубликована: Янв. 5, 2023

A chiral phosphoric acid-catalyzed enantioselective aza-Friedel-Crafts reaction of 5-aminopyrazole derivatives with cyclic ketimines attached to a neutral functional group is reported. This protocol allows the formation pyrazole-based C2-quaternary indolin-3-ones high enantioselectivities and regioselectivities. Moreover, gram-scale synthesis 5-aminopyrazole-based was performed, no decrease in yield enantioselectivity.

Язык: Английский

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Highly Chemo-, Site-, and Enantioseletive para C–H Aminoalkylation of N-Monosubstituted Aniline Derivatives Affording 3-Amino-2-oxindoles

Organic Letters, Год журнала: 2020, Номер 22(6), С. 2173 - 2177

Опубликована: Март 6, 2020

In general, enantioselective C–H functionalization of N-monosubstituted anilines is a highly challenging task owing to the competitive chemoselective N–H bond insertion reactions. this paper, we reported direct chemo-, site-, and para aminoalkylation aniline derivatives with isatin-derived ketimines in presence chiral phosphoric acids (CPAs) offered practical strategy for asymmetric containing bonds.

Язык: Английский

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Chiral Phosphoric Acid-Catalyzed Enantioselective Dearomative Electrophilic Hydrazination: Access to Chiral Aza-Quaternary Carbon Indolenines

ACS Catalysis, Год журнала: 2022, Номер 12(13), С. 7511 - 7516

Опубликована: Июнь 9, 2022

Direct enantioselective synthesis of chiral aza-quaternary carbon indolenines through the dearomative electrophilic hydrazination 2,3-disubstituted indoles has been achieved. This catalytic asymmetric strategy leads to efficient construction a series enantioenriched in high yields and excellent stereoselectivities. The synthetic practicality this reaction demonstrated by modification derivatization drug molecules. In-situ infrared density functional theory calculations suggest that our system could overcome background achieve effective dearomatization.

Язык: Английский

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General, Modular Access toward Immobilized Chiral Phosphoric Acid Catalysts and Their Application in Flow Chemistry

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 5550 - 5559

Опубликована: Март 29, 2024

Chiral phosphoric acids (CPAs) are among the most frequently used organocatalysts, with an ever-increasing number of applications. However, these catalysts only obtained in a multistep synthesis and poorly recyclable, which significantly deteriorates their environmental economic performance. We herein report conceptually different, general strategy for direct immobilization CPAs on broad scope solid supports including silica, polystyrene, aluminum oxide. Solid-state were high yields thoroughly characterized elemental analysis by inductively coupled plasma-optical emission spectrometry (ICP-OES), nitrogen sorption measurements, thermogravimetric analysis, scanning transmission electron microscopy/energy-dispersive X-ray spectroscopy (STEM/EDX) images, solid-state NMR spectroscopy. Further, immobilized applied to variety synthetically valuable, highly stereoselective transformations under batch flow conditions transfer hydrogenations, Friedländer condensation/transfer hydrogenation sequence, Mannich reactions cryogenic conditions. Generally, stereoselectivities observed along robust catalyst stability reusability. After being 10 runs conditions, no loss selectivity or catalytic activity was observed. Under continuous-flow heterogeneous system operation 19 h enantioselectivity remained unchanged throughout entire process. expect our approach extend applicability higher level, focus chemistry more environmentally friendly resource-efficient use powerful catalysts.

Язык: Английский

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Rhodium(II)-Catalyzed Regioselective Remote C–H Alkylation of Protic Indoles

ACS Catalysis, Год журнала: 2021, Номер 11(9), С. 4929 - 4935

Опубликована: Апрель 8, 2021

Control of regioselectivity that defies the intrinsic reactivity arene C–H bonds remains a formidable challenge. In this work, dimeric Rh(II) complexes have been applied as an efficient catalyst for regioselective coupling NH indoles with diazo compounds. Two-substituted mostly reacted C(6) selectivity. Mechanistic studies revealed results from hydrogen-bonding directing effect, and C–C bond formation proceeds via Friedel–Crafts-type attack indole toward carbene species. contrast, reaction 4-methoxyindoles occurred exclusively complementary C(7)

Язык: Английский

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Diversity‐Oriented Catalytic Asymmetric Dearomatization of Indoles with o‐Quinone Diimides

Advanced Science, Год журнала: 2023, Номер 10(35)

Опубликована: Окт. 23, 2023

Abstract Herein, the first diversity‐oriented catalytic asymmetric dearomatization of indoles with o ‐quinone diimides ( ‐QDIs) is reported. The (CADA) one research focuses in terms structural and biological importance dearomatized indole derivatives. Although great achievements have been made target‐oriented CADA reactions, reactions are regarded as more challenging remain elusive due to lack synthons featuring multiple reaction sites difficulty precise control chemo‐, regio‐, enantio‐selectivity. In this work, ‐QDIs employed a versatile building block, enabling chemo‐divergent dearomative arylation [4 + 2] cycloaddition indoles. Under catalysis chiral phosphoric acid mild conditions, various indolenines, furoindolines/pyrroloindolines, six‐membered‐ring fused indolines collectively prepared good yields excellent enantioselectivities. This synthesis protocol enriches chemistry offers new opportunities for reactions.

Язык: Английский

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Enantioselective construction of chiral gem-difluorinated C2-quaternary indoline via dual MgSO₄–CPA-catalyzed asymmetric Mannich reactions

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(5), С. 1430 - 1436

Опубликована: Янв. 1, 2024

Herein, the synthesis of 2-(3,3-difluoro-2-phenylindolin-2-yl)-1-phenylethan-1-one scaffolds through asymmetric Mannich reactions between 3,3-difluoro cyclic ketimines and simple ketones is described.

Язык: Английский

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Organocatalytic dimensions to the C–H functionalization of the carbocyclic core in indoles: a review update

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(10), С. 2343 - 2365

Опубликована: Янв. 1, 2021

A review highlighting important research findings in remote C–H activation processes using effectual organocatalytic perspectives. The challenging indole carbocyclic ring positions were successfully accessed with proper regio- and stereocontrols.

Язык: Английский

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