Design and catalytic atroposelective synthesis of axially chiral isochromenone-indoles

Science China Chemistry, Journal Year: 2022, Volume and Issue: 65(10), P. 1929 - 1937

Published: Sept. 13, 2022

Language: Английский

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Advances in Catalytic Asymmetric Reactions Using 2-Indolylmethanols as Platform Molecules

Chinese Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 42(10), P. 3351 - 3351

Published: Jan. 1, 2022

Indole-based chiral heterocycles constitute a class of important heterocyclic compounds that are found in numerous natural products, pharmaceuticals, pesticide, and functional materials.The efficient highly enantioselective synthesis indole derivatives has become one the most issues organic chemistry.Due to simple reactivity traditional indoles, their involved catalytic asymmetric reactions very limited, resulting limited types constructed indole-based frameworks.To solve these challenging issues, chemists devised strategy introducing groups ring, so as obtain series functionalized derivatives, namely platform molecules, building blocks for constructing indole-related frameworks.Among them, 2-indolylmethanols which were designed on consideration introduction hydroxymethyl group C2-position ring would change reactive site ring.This molecules can act either electrophiles or nucleophiles, multi-carbon reactions.Therefore, design development have provided new derivatives.The advances using summarized, will open window designing application molecules.

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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Chiral Brønsted Acid Catalyzed Enantioselective Synthesis of Spiro-Isoindolinone-Indolines via Formal [3 + 2] Cycloaddition

Organic Letters, Journal Year: 2022, Volume and Issue: 24(18), P. 3319 - 3324

Published: May 4, 2022

A novel organocatalytic asymmetric formal [3 + 2] cycloaddition of 3-substituted 1H-indoles with in situ generated 3-hydroxy-isoindolinone-derived β,γ-alkynyl-α-ketimines has been developed. variety biologically relevant chiral spiro-isoindolinone-indolines were achieved excellent yields (up to 99%) and enantioselectivity 99% ee) under mild conditions. The gram-scale reaction this methodology several interesting transformations the products have demonstrated.

Language: Английский

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Organocatalytic Enantioselective 1,8-Addition for the Synthesis of Chiral Tetraarylmethanes from 2-Naphthol/Naphthalen-2-amine-Based Tertiary Alcohols

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(26), P. 14562 - 14569

Published: June 21, 2023

Catalytic enantioselective construction of optically active tetraarylmethanes remains a challenging issue in the field asymmetric synthesis because overwhelming steric hindrance and formidable stereocontrol that existed all-aryl-substituted quaternary carbon stereocenter. Here, we reported an organocatalytic chiral from racemic tertiary alcohols. With aid phosphoric acid catalyst, 6-methylenenaphthalen-2(6H)-ones were generated situ 6-(hydroxydiarylmethyl)naphthalen-2-ols, followed by stereoselective 1,8-conjugate addition to afford corresponding high excellent yields with enantioselectivities. Furthermore, scope alcohols has been successfully enlarged 6-(hydroxydiphenylmethyl)naphthalen-2-amines. Notably, it is first time use 2-naphthol/naphthalen-2-amine unit as auxiliary group generate α,β,γ,δ,ε,ζ-conjugate systems, which have involved remote stereocontrolled reactions. Particularly, stereoconvergent formal nucleophilic substitution reaction triarylmethanols achieved for tetraarylmethanes. In addition, DFT calculations applied provide guidance design additional understand origin stereoselectivity.

Language: Английский

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Palladium-Catalyzed Asymmetric Decarboxylation of 5-Vinyloxazolidine-2,4-Diones Triggering the Dearomatization of Electron-Deficient Indoles for the Synthesis of Chiral Highly Functionalized Pyrroloindolines

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3310 - 3315

Published: April 8, 2024

A catalyst system consisting of a chiral phosphoramidite ligand and Pd2(dba)3·CHCl3 causes the decarboxylation 5-vinyloxazolidine-2,4-diones to generate amide-containing aza-π-allylpalladium 1,3-dipole intermediates, which are capable triggering dearomatization 3-nitroindoles for diastereo- enantioselective [3+2] cycloaddition, leading formation series highly functionalized pyrroloindolines containing three contiguous stereogenic centers with excellent results (up 99% yield, 88:12 dr, 96% ee).

Language: Английский

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Catalyst-Controlled Divergent Reactions of 2,3-Disubstituted Indoles with Propargylic Alcohols: Synthesis of 3H-Benzo[b]azepines and Axially Chiral Tetrasubstituted Allenes

Organic Letters, Journal Year: 2022, Volume and Issue: 24(35), P. 6472 - 6476

Published: Aug. 30, 2022

Catalyst-controlled divergent reactions of 2,3-disubstituted indoles with propargylic alcohols were developed for the first time. In presence TsOH or B(C6F5)3 as catalyst, reacted smoothly 3-alkynyl-3-hydroxyisoindolinones to afford 3H-benzo[b]azepines by selective C2(sp2)-C3(sp2) ring expansion indoles. contrast, decreasing catalyst strength (e.g., chiral phosphoric acid) interrupted cascade reactions, affording axially tetrasubstituted allenes bearing an adjacent quaternary carbon stereocenter. Control experiments provided insights into reaction mechanism.

Language: Английский

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Aza‐Ortho‐Quinone Methides as Reactive Intermediates: Generation and Utility in Contemporary Asymmetric Synthesis

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(46)

Published: June 2, 2022

Abstract The aza‐ ortho ‐quinone methide (aza‐ o ‐QM) chemistry has overwhelmingly progressed in the past few decades. This review aims to integrate various transition metal‐catalyzed and organocatalytic strategies taming aza ‐o‐ QM intermediates, including ‐vinylidene quinone ‐VQM), ‐alkynyl ‐AQM), para p ‐QM), indole‐based ‐QM analog. These transient species are often utilized for direct enantioselective synthesis of complex (hetero)polycyclic or fused‐ring molecular scaffolds such as tetrahydroquinoline indoline, among others, which abundant many natural products, bioactive compounds, pharmaceuticals.

Language: Английский

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Brønsted acid-catalyzed asymmetric dearomatization of indolyl ynamides: Practical and enantioselective synthesis of polycyclic indolines

Chinese Chemical Letters, Journal Year: 2022, Volume and Issue: 34(3), P. 107647 - 107647

Published: July 2, 2022

Language: Английский

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