From Carbamate to Chalcone: Consecutive Anionic Fries Rearrangement, Anionic Si → C Alkyl Rearrangement, and Claisen–Schmidt Condensation

Kumar, Santosh; Bavikar, Suhas Ravindra; Kumar, Chebolu Naga Sesha Sai Pavan; Yu, Isaac Furay; Chein, Rong‐Jie

doi:10.1021/acs.orglett.8b02269

Cited by 18 publications

(15 citation statements)

References 47 publications

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“…10 We have also combined this method with Claisen-Schmidt condensation and demonstrated its practical application in the synthesis of natural products and pharmaceuticals. 11 In this Account, we describe the potential of both sulfide and silicon as valuable reagents for organic synthesis and emphasize the importance of exploring new reaction This document was downloaded for personal use only. Unauthorized distribution is strictly prohibited.…”

Section: Account Synlettmentioning

confidence: 99%

Exploring the Power of Sulfur, Silicon, and Organocatalysis: Innovative Strategies for Asymmetric Synthesis and Advanced Synthetic Methodology

Chein

Chiu

2023

Synlett

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This research account describes the development of chiral organocatalysts, focusing on diphenyl-2-pyrrolidinemethanol and its derivatives as valuable tools in asymmetric transformations. The research also includes the discovery of a novel anionic Si→C alkyl migration method, which has been developed into a one-pot procedure for synthesizing (E)-chalcones from hydroxyamide and N,N-diethylcarbamates. The findings underscore the potential of sulfide and silicon as valuable reagents for organic synthesis and emphasize the importance of exploring new reaction pathways and mechanisms to discover novel synthetic methods.

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Section: Account Synlettmentioning

confidence: 99%

Exploring the Power of Sulfur, Silicon, and Organocatalysis: Innovative Strategies for Asymmetric Synthesis and Advanced Synthetic Methodology

Chein

Chiu

2023

Synlett

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“…This is an aldolization-crotonization reaction between acetophenone derivatives with aromatic aldehydes. Reaction takes place in strongly acidic or basic catalysis under homogeneous conditions [149][150][151][152]. Use of an alkaline medium is more efficient for obtaining chalcones [153].…”

Section: Claisen-schmidt Reactionmentioning

confidence: 99%

Anticancer Activity of Natural and Synthetic Chalcones

Constantinescu

Lungu²

2021

IJMS

103

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Cancer is a condition caused by many mechanisms (genetic, immune, oxidation, and inflammatory). Anticancer therapy aims to destroy or stop the growth of cancer cells. Resistance to treatment is theleading cause of the inefficiency of current standard therapies. Targeted therapies are the most effective due to the low number of side effects and low resistance. Among the small molecule natural compounds, flavonoids are of particular interest for theidentification of new anticancer agents. Chalcones are precursors to all flavonoids and have many biological activities. The anticancer activity of chalcones is due to the ability of these compounds to act on many targets. Natural chalcones, such as licochalcones, xanthohumol (XN), panduretin (PA), and loncocarpine, have been extensively studied and modulated. Modification of the basic structure of chalcones in order to obtain compounds with superior cytotoxic properties has been performed by modulating the aromatic residues, replacing aromatic residues with heterocycles, and obtaining hybrid molecules. A huge number of chalcone derivatives with residues such as diaryl ether, sulfonamide, and amine have been obtained, their presence being favorable for anticancer activity. Modification of the amino group in the structure of aminochalconesis always favorable for antitumor activity. This is why hybrid molecules of chalcones with different nitrogen hetercycles in the molecule have been obtained. From these, azoles (imidazole, oxazoles, tetrazoles, thiazoles, 1,2,3-triazoles, and 1,2,4-triazoles) are of particular importance for the identification of new anticancer agents.

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“…The anionic version of this process, also known as the Snieckus–Fries rearrangement, was pioneered by Snieckus in 1983 . o-Lithiated O -aryl N , N -dialkylcarbamates are not stable in the face of an increase of temperature evolving through an O → C 1,3-carbamoyl rearrangement that provides salicylamide derivatives and a variety of useful synthetic transformations . The rate of this anionic ortho-Fries (A o F) rearrangement mainly depends on the presence of additional functional groups on the aromatic ring and on the nature of the N-substituents .…”

Section: Introductionmentioning

confidence: 99%

Experimental and Computational Study of the 1,5-O → N Carbamoyl Snieckus–Fries-Type Rearrangement

et al. 2020

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The reactions of o-lithiated O-aryl N,N-diethylcarbamates with different CN multiple bond electrophiles have been thoroughly studied. A 1,5-O→N carbamoyl shift, a new variation of the anionic Fries-type rearrangement, takes place when nitriles, imines or alkylcarbodiimides are employed. In these cases, the carbamoyl group plays a dual role as directing group and building up a variety of functional groups through the 1,5-O→N carbamoyl migration. On the other hand, the use of iso(thio)cyanates and arylcarbodiimides led to non-rearranged o-functionalized O-arylcarbamates.This reactivity was further computationally explored, and the governing factor could be traced back to the relative basicity of the alternative products (migrated vs non-migrated substrates). This exploration also provided interesting insight about the degree of complexation of the lithium cation onto these substrates. A new access to useful 2-hydroxybenzophenone derivatives has also been developed.

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From Carbamate to Chalcone: Consecutive Anionic Fries Rearrangement, Anionic Si → C Alkyl Rearrangement, and Claisen–Schmidt Condensation

Cited by 18 publications

References 47 publications

Exploring the Power of Sulfur, Silicon, and Organocatalysis: Innovative Strategies for Asymmetric Synthesis and Advanced Synthetic Methodology

Exploring the Power of Sulfur, Silicon, and Organocatalysis: Innovative Strategies for Asymmetric Synthesis and Advanced Synthetic Methodology

Anticancer Activity of Natural and Synthetic Chalcones

Experimental and Computational Study of the 1,5-O → N Carbamoyl Snieckus–Fries-Type Rearrangement

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