Enantio‐ and Diastereodivergent Synthesis of Spirocycles through Dual‐Metal‐Catalyzed [3+2] Annulation of 2‐Vinyloxiranes with Nucleophilic Dipoles

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(47), P. 24941 - 24949

Published: Sept. 17, 2021

The development of efficient and straightforward methods for obtaining all optically active isomers structurally rigid spirocycles from readily available starting materials is great value in drug discovery chiral ligand development. However, the stereodivergent synthesis bearing multiple stereocenters remains an unsolved challenge owing to steric hindrance ring strain. Herein, we report enantio- diastereodivergent through dual-metal-catalyzed [3+2] annulation oxy π-allyl metallic dipoles with less commonly employed nucleophilic (imino esters). A series spiro compounds a pyrroline olefin were easily synthesized manner (up 19:1 dr, >99 % ee), which showed promise as new type N-olefin ligand. Preliminary mechanistic studies also carried out understand process this bimetallic catalysis.

Language: Английский

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Atroposelective Synthesis of 1,1′‐Bipyrroles Bearing a Chiral N−N Axis: Chiral Phosphoric Acid Catalysis with Lewis Acid Induced Enantiodivergence

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(16)

Published: Feb. 17, 2022

Abstract We present herein a highly efficient atroposelective synthesis of axially chiral 1,1′‐bipyrroles bearing an N−N linkage from simple hydrazine and 1,4‐diones. Further product derivatizations led to bifunctional compounds with high potential in asymmetric catalysis. For this chrial phosphoric acid (CPA)‐catalyzed double Paal–Knorr reaction, intriguing Fe(OTf) 3 ‐induced enantiodivergence was also observed.

Language: Английский

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Advances in Palladium‐Catalyzed Decarboxylative Cycloadditions of Cyclic Carbonates, Carbamates and Lactones

ChemCatChem, Journal Year: 2022, Volume and Issue: 14(9)

Published: Jan. 31, 2022

Abstract Palladium‐catalyzed decarboxylative cycloadditions have emerged as highly effective methods for constructing structurally diverse carbo‐ and heterocycles because of the formation at least two carbon‐carbon or carbon‐heteroatom bonds in a single step. It is great interest to chemists that this type cycloaddition reactions possesses some special advantages such high reactivity, exclusive regioselectivity, good functional group compatibility. Based on these qualities, palladium‐catalyzed present strong ability synthetic chemistry been flourished especially last five years. In review, achievements involving cyclic carbonates, carbamates, lactones accessing oxacyclo‐, azacyclo‐ carbocyclic compounds are addressed. Mechanistic insights applications toward synthesis natural products discussed. The challenges opportunities field also outlined.

Language: Английский

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Atroposelective Construction of Nine‐Membered Carbonate‐Bridged Biaryls

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 27, 2022

Abstract We herein demonstrated an efficient method for the atroposelective construction of nine‐membered carbonate‐bridged biaryls through vinylidene ortho ‐quinone methide (VQM) intermediates. Diverse products with desirable pharmacological features were synthesized in satisfying yields and good to excellent enantioselectivities. In subsequent bioassays, several agents showed considerable antiproliferative activity via mitochondrial‐related apoptosis mechanism. Further transformations produced more structural diversity may inspire new ideas developing functional molecules.

Language: Английский

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Temperature-Controlled Divergent Asymmetric Synthesis of Indole-Based Medium-Sized Heterocycles through Palladium Catalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(2), P. 1164 - 1172

Published: Jan. 4, 2023

The divergent construction of chiral medium-sized rings is an essential but challenging task in organic synthesis. Herein, we report a temperature-controlled catalytic system for the divergent, enantioselective synthesis different types starting from same substrate set. Enabled by planar bisphosphine ligand, palladium-catalyzed (5 + 4) and formal 2) annulations cyclic aza-dienes vinylethylene carbonates proceeded smoothly to afford broad spectrum indole-based heterocycles excellent yields with outstanding enantioselectivities. Those products could be further diversified through various functional group transformations. Moreover, mechanistic studies, including control experiments DFT calculations, shed light on understanding observed regio- enantioselectivities n) cyclization.

Language: Английский

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Fungicide-inspired precursors of π-allylpalladium intermediates for palladium-catalyzed decarboxylative cycloadditions

Chemical Science, Journal Year: 2023, Volume and Issue: 14(11), P. 3024 - 3029

Published: Jan. 1, 2023

Inspired by a fungicide, we designed 5-vinyloxazolidine-2,4-diones as new precursors of π-allylpalladium zwitterionic intermediates and developed palladium-catalyzed asymmetric (5 + 3) cycloaddition with azomethine imines (3 2) 1,1-dicyanoalkenes. Both reactions proceeded smoothly under mild reaction conditions to produce various chiral heterocyclic compounds in high yields excellent enantioselectivities. These results revealed that were type suitable precursor for palladium catalysis will find extensive applications Pd-catalyzed such allylic alkylation.

Language: Английский

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Recent advances of Pd-π-allyl zwitterions in cycloaddition reactions

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 34(11), P. 108401 - 108401

Published: March 30, 2023

Language: Английский

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Asymmetric synthesis of spirofuro[2,3-b]azepine-5,3′-indoline derivativesviacycloisomerization/[4 + 3] annulation process under Au/N-heterocyclic carbene relay catalysis

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(13), P. 3347 - 3352

Published: Jan. 1, 2023

A variety of enantioenriched spirofuro[2,3- b ]azepine-5,3’-indoline derivatives were synthesized via Au(I)/chiral NHC relay catalyzed cycloisomerization/asymmetric [4+3] annulation.

Language: Английский

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Synthesis of Chiral Endocyclic Allenes and Alkynes via Pd-Catalyzed Asymmetric Higher-Order Dipolar Cycloaddition

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

Published: Sept. 18, 2024

A Pd-catalyzed asymmetric higher-order dipolar cycloaddition between allenyl carbonates and azadienes is achieved by exploiting novel alkylidene-π-allyl-Pd dipoles. This research provides a modular platform for the synthesis of challenging chiral endocyclic allenes bearing medium-sized heterocyclic motif centrally stereocenter in good yields with high enantio- diastereoselectivities (29 examples, up to 97% yield, 97:3 er >19:1 dr). Experimental computational studies elucidate possible reaction mechanism observed stereochemical results. Based on mechanistic understanding, new π-propargyl-Pd dipole was designed further extend success higher order strategy 10-membered alkynes from propargyl (13 98% yield 94.5:5.5 er).

Language: Английский

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Asymmetric Three-Component Reaction of Enynal with Alcohol and Imine as An Expeditious Track to Afford Chiral α-Furyl-β-amino Carboxylate Derivatives

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(22), P. 14185 - 14193

Published: Nov. 4, 2022

Herein, we report an achiral dirhodium complex and chiral phosphoric acid cooperatively catalyzed asymmetric three-component reaction of enynal with alcohol imine, affording α-furyl-β-amino carboxylates in good to high yields generally excellent stereoselectivity. The successful introduction as a carbene precursor this provides expeditious track prepare furan derivatives adjacent quaternary tertiary stereocenters. starting materials are stable readily available, the method features 100% atom economy bond-formation efficiency. This is highly enantioselective gem-difunctionalization metal generated situ from enynal. These products could be smoothly converted polycyclic frameworks drug-conjugated through different cycloaddition reactions.

Language: Английский

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