Quinone methides and indole imine methides as intermediates in enantioselective catalysis

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(6), P. 426 - 438

Published: June 6, 2022

Language: Английский

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Construction of Oxygen‐ and Nitrogen‐based Heterocycles from p‐Quinone Methides

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(12), P. 4150 - 4173

Published: Aug. 9, 2021

In the last few years, there has been an explosive growth in area of para-quinone methide (p-QM) chemistry. This boom is actually due to unique reactivity pattern p-QMs, and also their remarkable synthetic applications. fact, p-QMs serve as synthons for unsymmetrical diaryl- triarylmethanes, construction diverse range carbocycles heterocycles. a wide structurally complex heterocyclic frameworks could be accessed through transformations modified stable p-QMs. Therefore, main focus this review article cover recent advancements transition-metal, Lewis acid base-catalyzed/mediated p-quinone methides (p-QMs) oxygen- nitrogen-containing

Language: Английский

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Design and Application of m‐Hydroxybenzyl Alcohols in Regioselective (3 + 3) Cycloadditions of 2‐Indolymethanols^†

Chinese Journal of Chemistry, Journal Year: 2022, Volume and Issue: 41(1), P. 27 - 36

Published: Sept. 16, 2022

Comprehensive Summary A new class of m ‐hydroxybenzyl alcohols has been designed as competent three‐carbon building blocks and achieved their application in 2‐indolylmethanol‐involved regioselective (3 + 3) cycloadditions under the catalysis Brønsted acids. By this appoach, a series indole‐fused six‐membered cycloadducts have synthesized overall good yields (up to 98%) with excellent regioselectivity (all >95: 5 rr), thus affording powerful method for construction rings. Moreover, catalytic asymmetric version cycloaddition preliminarily investigated, which revealed potential reaction constructing chiral rings an enantioselective manner. This work not only accomplished first design reactants, but also represents cycloadditions. In addition, provides example C3‐nucleophilic 2‐indolylmethanols, will substantially enrich chemistry 2‐indolylmethanols.

Language: Английский

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Asymmetric Synthesis of Remotely Chiral Naphthols and Naphthylamines via Naphthoquinone Methides

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(23), P. 12802 - 12811

Published: June 5, 2023

Quinone methides are well-established intermediates in asymmetric synthesis. In contrast, their extended analogues with the carbonyl and methide units distributed across two different rings have not been exploited Herein, we achieved first process involving such intermediates. Specifically, use of suitable chiral phosphoric acids enabled situ generation 2-naphthoquinone 8-methides corresponding aza counterparts for mild one-pot nucleophilic addition. These processes provided rapid access to a wide range previously less accessible remotely naphthols naphthylamines both high efficiency excellent enantioselectivity. Control experiment DFT calculations important insights into reaction mechanism, which likely involves acid molecules enantiodetermining transition states. This work serves as proof concept exploitation new types quinone versatile synthesis, thus providing platform efficient construction remote benzylic stereogenic centers aromatic compounds.

Language: Английский

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Optogenetics with Atomic Precision─A Comprehensive Review of Optical Control of Protein Function through Genetic Code Expansion

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 10, 2025

Conditional control of protein activity is important in order to elucidate the particular functions and interactions proteins, their regulators, substrates, as well impact on behavior a cell or organism. Optical provides perhaps optimal means introducing spatiotemporal over function it allows for tunable, rapid, noninvasive activation its native environment. One method optical through introduction photocaged photoswitchable noncanonical amino acids (ncAAs) genetic code expansion cells animals. Genetic incorporation photoactive ncAAs at key residues tool activation, sometimes deactivation, activity. Importantly, site can typically be rationally selected based structural, mechanistic, computational information. In this review, we comprehensively summarize applications lysine, tyrosine, cysteine, serine, histidine, glutamate, aspartate derivatives, phenylalanine analogues. The extensive diverse list proteins that have been placed under demonstrates broad applicability methodology.

Language: Английский

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Visible light and base promoted O-H insertion/cyclization of para-quinone methides with aryl diazoacetates: An approach to 2,3-dihydrobenzofuran derivatives

Chinese Chemical Letters, Journal Year: 2021, Volume and Issue: 32(8), P. 2577 - 2581

Published: March 7, 2021

Language: Английский

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Merging dearomatization with redox-neutral C(sp³)–H functionalization via hydride transfer/cyclization: recent advances and perspectives

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(18), P. 5041 - 5052

Published: Jan. 1, 2022

This review highlights the encouraging advances in hydride transfer-involved dearomatization reaction during past decade, content of which is categorized according to acceptors, namely vinylogous imines and quinone methides.

Language: Английский

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Chiral Brønsted acid-catalyzed asymmetric intermolecular [4 + 2] annulation of ynamides with para-quinone methides

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(5), P. 1467 - 1473

Published: April 12, 2023

Language: Английский

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Synthesis of Fluorine-Containing Multisubstituted Oxa-Spiro[4,5]cyclohexadienones via a Fluorinated Alcohol-Catalyzed One-Pot Sequential Cascade Strategy

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 2847 - 2857

Published: Feb. 16, 2024

In recent years, the application of fluorinated alcohols as solvents, cosolvents, or additives has become important in modern organic synthesis. However, their potential efficient catalysts synthesis not been well-explored. this article, we report on development a one-pot sequential cascade reaction p-quinone methides with difluoroenoxysilanes using hexafluoroisopropanol catalyst. This allows for preparation multisubstituted oxa-spiro[4,5]cyclohexadienones. By 50 mol % 1,1,1,3,3,3-Hexafluoroisopropanol (HFIP), proceeds smoothly to yield 1,6-conjugated products, which are then subjected oxidative dearomatization/hemiacetalization PhI(OAc)2. The overall process affords moderate high yields and excellent diastereoselectivities.

Language: Английский

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P(NMe₂)₃-Mediated Umpolung Spirocyclopropanation Reaction of p-Quinone Methides: Diastereoselective Synthesis of Spirocyclopropane-Cyclohexadienones

Organic Letters, Journal Year: 2020, Volume and Issue: 22(21), P. 8376 - 8381

Published: Oct. 12, 2020

An unprecedented umpolung spirocyclopropanation reaction of p-quinone methides and α-keto carbonyls is described. Our strategy based on 1,6-conjugate addition intramolecular nucleophilic substitution offers a new method for effective access to series highly functionalized spirocyclohexadienonyl cyclopropanes having two vicinal quaternary carbons in ≤98% yield >20:1 dr. Significantly, cyclic acyclic topological structures as 1,1-dipole one-carbon synthons have distinct influence the stereochemistry products, showing reversal diastereoselectivity this P(NMe2)3-mediated spirocyclopropanation.

Language: Английский

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