Chiral Spirocyclic Phosphoric Acids and Their Growing Applications

Chinese Journal of Chemistry, Journal Year: 2020, Volume and Issue: 39(4), P. 802 - 824

Published: Oct. 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.

Language: 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, Journal Year: 2022, Volume and Issue: 9(22), P. 6331 - 6399

Published: Jan. 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.

Language: 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, Journal Year: 2023, Volume and Issue: 29(20)

Published: Jan. 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.

Language: 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, Journal Year: 2020, Volume and Issue: 22(6), P. 2173 - 2177

Published: March 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.

Language: Английский

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

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(13), P. 7511 - 7516

Published: June 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.

Language: Английский

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

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 5550 - 5559

Published: March 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.

Language: Английский

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

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(9), P. 4929 - 4935

Published: April 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)

Language: Английский

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

Advanced Science, Journal Year: 2023, Volume and Issue: 10(35)

Published: Oct. 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.

Language: 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, Journal Year: 2024, Volume and Issue: 11(5), P. 1430 - 1436

Published: Jan. 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.

Language: Английский

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Enantioselective Synthesis of Chiral 2,2-Difluoro-spiroindanone-dihydroquinazolinones by CPA-Catalyzed Cyclization Reactions

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

Published: Jan. 25, 2025

The synthesis of chiral gem-difluorinated spiro-heterocyclic compounds continues to be a significant challenge in organic chemistry due their widespread applications across various fields. Therefore, efficient asymmetric approaches for the spiroindanone-dihydroquinazolinones are particularly valuable, especially industrial manufacturing fluorinated drugs. Herein, we developed CPA-catalyzed enantioselective cyclization reactions gem-difluoroalkyl 1,3-indandiones with anthranilamides achieve 2,2-difluoro-spiroindanone-dihydroquinazolinones good high yields excellent enantioselectivities. Moreover, mechanism experiment proved that gem-difluoro substitution pattern promotes reaction.

Language: Английский

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