Conjugate addition of an ynone containing azulene with a tertiary amine

Yamaguchi, Junichi; Sugiyama, Satoko

doi:10.1016/j.tetlet.2016.08.094

Cited by 11 publications

(7 citation statements)

References 31 publications

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“…Recently, ynone 77 was prepared by oxidation of the sensitive alcohol 76 with 2,3dichloro-5,6-dicyano-1,4-quinone (DDQ) in high yield (not reported) (Scheme 19). 79 This ynone, containing the azulene moiety, can be decomposed by a strong oxidant such as Cr(VI) or Mn(VII).…”

Section: From Propargylic Alcoholsmentioning

confidence: 99%

“…Ammonia and a large variety of primary and secondary amines have been reacted with a range of ynones and furnished enaminones with a considerable structural variation. In general, the products are stable and formed in very good yields, except when (a) tertiary amines are applied, 79,349,350 (b) the substrate contains a nucleophile that can attack the primary product (enaminone), 351,352 and (c) primary amines are applied and the resulting products contain an electrophilic center that can react with the nitrogen in the enaminone moiety. 152,353 Furthermore, the reaction is stereoselective in most cases.…”

Section: Conjugate Additionsmentioning

confidence: 99%

“…When the diethoxymethyl moiety in 350 was replaced by an azulen-9-yl group 352, the course of the reaction with tertiary amines changed. 79 The first step was still conjugate addition of the amine, but a Hofmann elimination then occurred and gave the corresponding β-diethylaminoenone (353), as expected with E stereochemistry, in excellent yield under the best conditions (Scheme 161). No trimerization was observed, probably due to a higher electrophilicity of the carbonyl group and the significant excess of amine used by Yamaguchi and Sugiyama.…”

Section: Conjugate Additionsmentioning

confidence: 99%

“…No trimerization was observed, probably due to a higher electrophilicity of the carbonyl group and the significant excess of amine used by Yamaguchi and Sugiyama. 79 The yield appeared to be amine dependent, and when the amine contained different alkyl groups, several enaminones were formed. Intermediates I−III have been proposed to take part in the process.…”

Section: Conjugate Additionsmentioning

confidence: 99%

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Conjugated Ynones in Organic Synthesis

2019

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This review article will consider the preparation and application of ynones in synthetic organic chemistry. Concerning the preparation of these bifunctional compounds, several methodologies starting from propargyl alcohols, acyl derivatives, both by using alkynylmetal reagents or by transition metal (mainly palladium and copper) catalyzed alkynylations, carbon monoxide (carbonylation of terminal alkynes and alkenes), and other substrates will be discussed. The reactivity and synthetic applications of ynones will be focused on conjugate additions with boron-, carbon-, nitrogen-, oxygen-, and other heteroatom-containing nucleophiles, as well as radicals. Then, cycloaddition processes will include [2 + 2] cycloadditions, [3 + 2] 1,3-dipolar cycloadditions (with azides, nitrones, azomethine imines and ylides, nitrile oxides, diazo compounds, and other dipoles), and [4 + 2] cycloadditions (mainly Diels–Alder-type reactions). The reduction of the triple bond, addition to the carbonyl group (using carbon- and heteronucleophiles and reductions), and other not so commonly used processes (such as aldol reactions, cyclizations, and isomerizations) will be considered at the end.

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Section: From Propargylic Alcoholsmentioning

confidence: 99%

Section: Conjugate Additionsmentioning

confidence: 99%

Section: Conjugate Additionsmentioning

confidence: 99%

Section: Conjugate Additionsmentioning

confidence: 99%

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Conjugated Ynones in Organic Synthesis

2019

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“…Interestingly, ethylation at the thiazolidinedione (TZD) occurred to give 6 (14%) (entry 2). Yamaguchi et al reported the conjugate addition of an ynone-containing azulene with a tertiary amine [ 40 ]. We considered that products 5 and 6 resulted from a similar mechanism ( Schemes S1 and S2 ) and thus we reduced the amount of Et 3 N. When 3.0 equiv.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of a Coumarin-Based PPARγ Fluorescence Probe for Competitive Binding Assay

Yoshikawa¹,

Ishida²,

Ohashi³

et al. 2021

IJMS

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Peroxisome proliferator-activated receptor γ (PPARγ) is a molecular target of metabolic syndrome and inflammatory disease. PPARγ is an important nuclear receptor and numerous PPARγ ligands were developed to date; thus, efficient assay methods are important. Here, we investigated the incorporation of 7-diethylamino coumarin into the PPARγ agonist rosiglitazone and used the compound in a binding assay for PPARγ. PPARγ-ligand-incorporated 7-methoxycoumarin, 1, showed weak fluorescence intensity in a previous report. We synthesized PPARγ-ligand-incorporating coumarin, 2, in this report, and it enhanced the fluorescence intensity. The PPARγ ligand 2 maintained the rosiglitazone activity. The obtained partial agonist 6 appeared to act through a novel mechanism. The fluorescence intensity of 2 and 6 increased by binding to the ligand binding domain (LBD) of PPARγ and the affinity of reported PPARγ ligands were evaluated using the probe.

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Addition Reactions

Kočovský¹

2020

Organic Reaction Mechanisms · 2016

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Conjugate addition of an ynone containing azulene with a tertiary amine

Cited by 11 publications

References 31 publications

Conjugated Ynones in Organic Synthesis

Conjugated Ynones in Organic Synthesis

Synthesis of a Coumarin-Based PPARγ Fluorescence Probe for Competitive Binding Assay

Addition Reactions

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