Cu-Catalyzed Asymmetric 1,3-Dipolar Cycloaddition of N-2,2,2-Trifluoroethylisatin Ketimines Enables the Desymmetrization of N-Arylmaleimides: Access to Enantioenriched F₃C-Containing Octahydropyrrolo[3,4-c]pyrroles

Organic Letters, Journal Year: 2022, Volume and Issue: 24(22), P. 4052 - 4057

Published: May 27, 2022

With a Cu(OTf)2/chiral ferrocenyl P,N-ligand complex as catalyst, the enantioselective desymmetrization of N-arylmaleimides was successfully realized by taking advantage asymmetric 1,3-dipolar cycloaddition reaction N-2,2,2-trifluoroethylisatin ketimines. A series structurally diverse F3C-containing octahydropyrrolo[3,4-c]pyrroles, bearing four contiguous carbon stereocenters and one stereogenic chiral C-N axial bond, were obtained with excellent results (≤99% yield, >20:1 dr, 99% ee).

Language: Английский

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Recent Developments in Enantioselective Domino Reactions. Part B: First Row Metal Catalysts

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(6), P. 768 - 819

Published: Jan. 17, 2023

This review updates the field of enantioselective domino reactions promoted by chiral catalysts derived from first row metals, such as zinc, iron, copper, scandium, nickel, cobalt, titanium, chromium and magnesium special case, published since beginning 2019. It illustrates how much a diversity these allow an impressive range novel highly many types to be achieved, providing one-pot access very complex functionalized molecules simple starting materials.

Language: Английский

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Organocatalyzed asymmetric dearomative 1,3‐dipolar cycloaddition of 2‐nitrobenzofurans and N‐2,2,2‐trifluoroethylisatin ketimines

Chirality, Journal Year: 2022, Volume and Issue: 34(7), P. 1019 - 1034

Published: May 6, 2022

Abstract A readily available chiral cyclohexanediamine‐derived bifunctional tertiary amine‐squaramide catalyst is more effective for the asymmetric dearomative 1,3‐dipolar cycloaddition of 2‐nitrobenzofurans and N ‐2,2,2‐trifluoroethylisatin ketimines. range structurally diverse spiro‐fused polyheterocyclic compounds containing oxindole, pyrrolidine, hydrobenzofuran motifs were smoothly obtained in excellent results (up to 99% yield, >20:1 dr all cases up ee). This method features high efficiency, mild reaction conditions, exquisite induction, wide functional group tolerance, great potential scale‐up synthesis, attractive product diversification.

Language: Английский

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Synthesis of Benzofuro[3,2-b]indol-3-one Derivatives via Dearomative (3 + 2) Cycloaddition of 2-Nitrobenzofurans and para-Quinamines

Molecules, Journal Year: 2024, Volume and Issue: 29(5), P. 1163 - 1163

Published: March 5, 2024

An efficient dearomative (3 + 2) cycloaddition of para-quinamines and 2-nitrobenzofurans has been developed. This reaction proceeds smoothly under mild conditions affords a series benzofuro[3,2-b]indol-3-one derivatives in good to excellent yields (up 98%) with perfect diastereoselectivities (all cases > 20:1 dr). The scale-up synthesis versatile derivatizations demonstrate the potential synthetic application protocol. A plausible mechanism is also proposed account for observed process. work represents first instance N-triggered 2-nitrobenzofurans.

Language: Английский

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Dinuclear zinc catalyzed asymmetric [3 + 2] spiroannulation for the synthesis of diverse bispirocyclic saccharines

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(18), P. 5010 - 5015

Published: Jan. 1, 2022

A highly atom-economical and novel enantioselective [3 + 2] spiroannulation reaction of saccharine-derived cyclic 1-azadienes with α-hydroxy-1-indanones has been developed.

Language: Английский

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Recent Advances of N-2,2,2-Trifluoroethylisatin Ketimines in Organic Synthesis

Molecules, Journal Year: 2023, Volume and Issue: 28(7), P. 2990 - 2990

Published: March 27, 2023

The special properties of fluorine atoms and fluorine-containing groups have led to an increasing number applications for organic compounds, which are also extremely widely used in the field new drug development. Unfortunately, naturally fluorinated organics rare nature, so selective introduction or into molecules is very important pharmaceutical/synthetic chemists. N-2,2,2-trifluoroethylisatin ketimines received attention many chemists since they were first developed as synthons 2015. This paper reviews synthesis reactions trifluoroethyl isatin ketimine has been involved recent years, focusing on types stereoselectivity products, provides a prospect its application this field.

Language: Английский

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Recent Progress of Electron‐Withdrawing‐Group‐Tethered Arenes Involved Asymmetric Nucleophilic Aromatic Functionalizations

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(21), P. 3630 - 3650

Published: Oct. 3, 2022

Abstract Electron‐withdrawing groups (EWG) have emerged as a powerful tool for the activation of various arenes to promote nucleophilic dearomative additions construction complicated chiral cyclic structures under asymmetric catalytic systems. Nitro‐indoles, nitro‐benzofurans/benzothiophenes, and related nitro‐heteroarenes are widely applied in reaction with nucleophiles construct enantioenriched polycyclic skeletons via dearomatization process. Meanwhile, electron‐deficient azo‐group nitroso‐group an alternative arenes, which enable formal aromatic arylations electrophilic aromatics novel biaryl atropisomers. Besides, azo‐naphthanenes served dipolar surrogates dipolarophiles proceed cycloadditions skeletons. The EWG‐tethered arene has proven be versatile protocol structurally diversified backbones. This review summarizes latest progress involved transformations organo‐ or transition metal catalysis. magnified image

Language: Английский

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Asymmetric Metal‐Templated Approach to Amino Acids with a CF₃‐Containing 3,2’‐Pyrrolidinyl Spirooxindole Core via a Michael/Mannich [3+2]‐Cycloaddition Reaction

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(5), P. 1205 - 1211

Published: Dec. 12, 2023

Abstract We report here a practical protocol for the asymmetric synthesis of amino acids (AAs) with CF 3 ‐containing 3,2’‐pyrrolidinyl spirooxindole skeleton three defined carbon stereocenters via sequential Michael/Mannich [3+2]‐cycloaddition reaction. The coupling robust and stereochemically stable chiral dehydroalanine Ni(II) complex various N ‐2,2,2‐trifluoroethylisatin ketimines in presence triethylamine afforded library single diastereomeric complexes moiety 36–71% yields. In particular, change base to LiOH allowed obtain predominantly Michael addition product 76% yield. Finally, decomposition obtained HCl provided target AA core (2 S ,4 R )‐2,4‐diamino‐5,5,5‐trifluoropentanoic acid – an ( )‐norvaline derivative, together easy recovery auxiliary ligand starting complex.

Language: Английский

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Asymmetric decarboxylative [3 + 2] cycloaddition for the diastereo- and enantioselective synthesis of spiro[2.4]heptanes via cyclopropanation

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(8), P. 2121 - 2128

Published: Jan. 1, 2022

A novel asymmetric [3 + 2] cycloaddition reaction of 1,4-dipoles and nitroolefins catalysed by the cooperative action chiral palladium/phosphine complex urea-tertiary amine is described.

Language: Английский

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Metal-Free Diastereo- and Enantioselective Dearomative Formal [3 + 2] Cycloaddition of 2-Nitrobenzofurans and Isocyanoacetate Esters

Organic Letters, Journal Year: 2022, Volume and Issue: 24(11), P. 2149 - 2154

Published: March 16, 2022

The diastereo- and enantioselective dearomative formal [3 + 2] cycloaddition of 2-nitrobenzofurans α-aryl-α-isocyanoacetate esters provides tricyclic compounds bearing the 3

Language: Английский

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