Chiral Brønsted Acid-Catalyzed Intramolecular Asymmetric Dearomatization Reaction of Indoles with Cyclobutanones via Cascade Friedel–Crafts/Semipinacol Rearrangement

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25878 - 25887

Published: Sept. 3, 2024

The highly efficient synthesis of chiral indolines fused with an azabicyclo[2.2.1]heptanone moiety is achieved by asymmetric dearomatization reaction indoles cyclobutanones. A new imidodiphosphorimidate (IDPi) catalyst synthesized and exhibits extraordinary activity in promoting a cascade Friedel-Crafts/semipinacol rearrangement. Target molecules are prepared good yields (up to 95%) excellent enantioselectivity 98% ee) operational convenience. Combined experimental computational studies provide detailed mechanistic insights into the energy landscape origin stereochemical induction reaction.

Language: Английский

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Enantioselective Aminative Dearomatization of Indoles via Electrophilic 1,6-Addition of p-Quinone Diimides (p-QDIs)

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4932 - 4937

Published: June 3, 2024

Herein we report the first use of p-quinone diimide for aminative dearomatization 2,3-disubstituted indoles to furnish C3 aza-quaternary chiral indolenines. This approach, which proceeds via an electrophilic 1,6-addition diimide, allows synthesis array optically active indolenines with high yields and excellent enantioselectivities. A one-pot approach same has also been established further improve synthetic accessibility this protocol.

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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Catalytic Asymmetric Dearomative Arylation of 2‐Naphthols Enabled by o‐Quinone Diimides

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(20), P. 4238 - 4243

Published: March 16, 2024

Abstract The catalytic asymmetric dearomative arylation of 2‐naphthols enabled by the unconventional reactivity o ‐quinone diimides, i. e. 1,4‐conjugate addition on quinone sp 2 hybridized carbon, has been established. Under catalysis chiral phosphoric acid, various cyclohexaenones bearing an all‐carbon quaternary stereocenter have prepared with excellent yields and enantioselectivities.

Language: Английский

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Intermolecular Enantioselective Dearomative Oxidative Heck Reaction of Indoles

Acta Chimica Sinica, Journal Year: 2024, Volume and Issue: 82(1), P. 1 - 1

Published: Jan. 1, 2024

Transition-metal-catalyzed asymmetric dearomatization reaction represents a straightforward method to access chiral cyclic compounds.In recent years, enantioselective dearomative Heck reactions of indoles, benzofurans, pyrroles, furans, and naphthalenes have been successfully developed.Nevertheless, current reports are mainly limited the intramolecular reaction, intermolecular still underdeveloped.In consideration relatively mild conditions in oxidative we envisioned that its induction might be possible due commonly-proposed cationic rather than neutral mechanism for reaction.In present work, an palladium-catalyzed indoles with arylboronic acids has developed.By employing Pd(OAc)2 as catalyst precursor, pyridineoxazoline ligand, oxygen oxidant, benzoquinone (BQ) co-oxidant, series indolines bearing C2-substituted quaternary stereocenter were afforded moderate good yields ee values.A general procedure this is described following: To dried Schlenk tube charged (4.5 mg, 10 mol%) ligand L9 (15.1 20 under O2 atmosphere. 2 mL N-methylpyrrolidone (NMP) solvent was then introduced via syringe sealed using Teflon cap.The mixture stirred at 60 ℃ 30 min order form complex.After cooling room temperature, indole substrates 1 (0.2 mmol), aryl boronic (0.6 co-oxidant BQ (4.3 added system atmosphere.The resulting 80 12 h.When completed [monitored by thin-layer chromatography (TLC)], water extracted ethyl acetate.The combined organic phases over anhydrous Na2SO4 concentrated reduced pressure.The residue purified flash column on silica gel [V(ethyl acetate)∶V(petroleum ether)＝1∶ 15] afford products 2.

Language: Английский

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Intermolecular Asymmetric Arylative Dearomatization of 1-Naphthols

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

Arylative dearomatization forms quaternary stereocenters in cyclic systems with the concomitant introduction of an aromatic ring. Pd-catalyzed arylative dearomatization, which uses conditions analogous to cross-coupling, has emerged as a powerful method intramolecular context. But translating this from cyclizations intermolecular process proven extremely challenging: examples are scarce, and those that exist have not been rendered enantioselective, despite potential for broad application medicinal chemistry natural product synthesis. We describe strategy utilizes attractive interactions between ligand substrate overcome challenge promote intermolecular, highly enantioselective naphthols using range aryl bromide electrophiles. Crucial success is use readily accessed sulfonated chiral phosphine sSPhos, we believe engages electrostatic substrate. Not only does sSPhos control enantioselectivity but it also drastically accelerates reaction, most likely by facilitating challenging palladation step initiates dearomatization.

Language: Английский

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Regioselective N-arylation of N-Acylsulfenamides Enabled by o-Quinone Diimides

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

Published: Feb. 27, 2025

The functionalization of N-acylsulfenamides is a research focus in organosulfur chemistry, as the N-S array has unique properties and versatile applications. Although great progress been made S-functionalization, N-functionalization, especially N-arylation N-acylsulfenamides, rarely explored because lower nucleophilicity N-site. Herein, we report Brønsted acid-catalyzed regioselective reaction with o-quinone diimides. Under mild metal-free conditions, wide range N-arylated have prepared good yields excellent regioselectivity. ease gram-scale synthesis transformations into useful sulfonamides demonstrates their synthetic practicality.

Language: Английский

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Dearomative spiroannulation of indoles enabled by the diaza-[1,2]-Wittig rearrangement

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(6), P. 1685 - 1691

Published: Jan. 1, 2024

Reported herein is the first diaza-[1,2]-Wittig rearrangement-enabled dearomative spiroannulation reaction of indoles. This protocol features metal-free conditions, a redox-neutral process, broad substrate scope, and good yield.

Language: Английский

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Diastereodivergent and Regioselective Synthesis of Tetrahydrofuro[2,3-b]furans with Four Consecutive Stereocenters

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 4134 - 4144

Published: Feb. 23, 2024

Base-catalyzed diastereodivergent and regioselective domino processes of triketone enones with arylacetaldehydes for the synthesis tetrahydrofuro[2,3-

Language: Английский

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Azocarboxamide-enabled enantioselective regiodivergent unsymmetrical 1,2-diaminations

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 26, 2024

Language: Английский

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