Aromatic Amide‐Derived Non‐Biaryl Atropisomers as Highly Efficient Ligands in Silver‐Catalyzed Asymmetric Cycloaddition Reactions

Bai, Xing‐Feng; Song, Tao; Xu, Zheng; Xia, Chungu; Huang, Wei‐Sheng; Xu, Li‐Wen

doi:10.1002/ange.201501100

Cited by 23 publications

(3 citation statements)

References 94 publications

(16 reference statements)

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“…The structural and stereochemical assignments of the pyrrolidine derivatives were made by comparing with those found in the literature. Based on the observed stereochemistry of the products and the literature findings by Bai et al, 22,23 we propose the transition state shown in Figure 2. In this transition state, the CFAM4 ligand, imine, and the dipolarophile are coordinated to the silver ion in such a way that the cycloaddition takes place from the si-side of the imine nitrogen in an endo-mode.…”

Section: Resultssupporting

confidence: 63%

Asymmetric synthesis of aryl‐substituted pyrrolidines by using CFAM ligand–AgOAc chiral system via 1,3‐dipolar cycloaddition reaction

Beksultanova

Doğan

2023

Chirality

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We have prepared a ligand library based on a ferrocenyl aziridinyl methanol core unit (simply called FAM) having a phenyl group, a cyclohexyl group, and a naphthyl group to be used in 1,3-dipolar cycloaddition (1,3-DC) reactions for the synthesis of chiral pyrrolidines. These chiral ligands were used with AgOAc in 1,3-DC reactions taking place between the aryl-substituted azomethine ylides and N-methylmaleimide as the dipolarophile. In each case, the expected aryl-substituted pyrrolidines were obtained in good to excellent yields with acceptable enantioselectivities favoring only the endo product. The chiral catalyst system CFAM4-AgOAc was also used in 1,3-DC reaction with different dipolarophiles such as dimethyl maleate, tert-butyl acrylate, methyl acrylate, trans-chalcone, and vinyl sulfone. In each case, the cycloadducts were obtained in acceptable yields albeit with low ee. Fortunately, it was possible to increase the ee up to >99% upon crystallization.

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Section: Resultssupporting

confidence: 63%

Asymmetric synthesis of aryl‐substituted pyrrolidines by using CFAM ligand–AgOAc chiral system via 1,3‐dipolar cycloaddition reaction

Beksultanova

Doğan

2023

Chirality

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“…Inspired by their previous work on asymmetric [3 + 2] cycloadditions based on a Michael-addition-initiated cyclization reaction, 203 Xu et al 204 reported the Michael addition of glycine aldimino esters to chalcones using the Ag(I)/Xing-Phos (L63−AgOAc) catalyst, providing excellent outcomes (up to >20:1 dr and 97% ee; Scheme 42). The cyclization products were obtained with cis-isomers when the 1,4-addition products were further treated with HCl, which could be easily transformed to the trans-isomers under alkaline conditions.…”

Section: Conjugate Addition Of Aldehydes and Ketonesmentioning

confidence: 99%

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

2018

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The metal-catalyzed asymmetric conjugate addition (ACA) reaction has emerged as a general and powerful approach for the construction of optically active compounds and is among the most significant and useful reactions in synthetic organic chemistry. In recent years, great progress has been made in this area with the use of various chiral metal complexes based on different chiral ligands. This review provides comprehensive and critical information on the enantioselective 1,4-conjugate addition of nonorganometallic (soft) nucleophiles and their importance in synthetic applications. The literature is covered from the last 10 years, and a number of examples from before 2007 are included as background information. The review is divided into multiple parts according to the type of nucleophile involved in the reaction (such as C-, B-, O-, N-, S-, P-, and Si-centered nucleophiles) and metal catalyst systems used.

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“…[19] These unique non-biaryl atropisomers not only exist in bioactive molecules, but also can be used as chiral auxiliaries, ligands and catalysts. [20,21] However, compared to the well-established axially chiral biaryls, the asymmetric catalytic processes for the formation of atropisomeric amides are still underdeveloped (Scheme 1a). This may be attributed to the less stable axis and hence less rigid skeleton.…”

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confidence: 99%

Catalytic Heteroannulation for the Synthesis of Quinoline‐4‐Carboxamides Bearing Axial Chirality

et al. 2022

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An iron(III) triflate catalyzed Friedländer-type heteroannulation of 2-(2-aminophenyl)-N,N-dialkyl-2-oxoamides with α-methylene carbonyl derivatives has been established, allowing facile access to a range of biologically interesting quinoline-containing tertiary amides in good yields.Investigations into the configurational stability of products led to the identification of a new type of stable axially chiral quinoline-4-carboxamide bearing a sterically demanding phenylsulfonyl C3substituent. Subsequently, an enantioselective catalytic variant was attempted. The employment of copper(II) catalysis using a chiral bisoxazoline ligand was found to be capable of providing moderate enantiocontrol.

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Aromatic Amide‐Derived Non‐Biaryl Atropisomers as Highly Efficient Ligands in Silver‐Catalyzed Asymmetric Cycloaddition Reactions

Cited by 23 publications

References 94 publications

Asymmetric synthesis of aryl‐substituted pyrrolidines by using CFAM ligand–AgOAc chiral system via 1,3‐dipolar cycloaddition reaction

Asymmetric synthesis of aryl‐substituted pyrrolidines by using CFAM ligand–AgOAc chiral system via 1,3‐dipolar cycloaddition reaction

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

Catalytic Heteroannulation for the Synthesis of Quinoline‐4‐Carboxamides Bearing Axial Chirality

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