The synthesis of 11-13-membered diacetylenic and 18-membered tetraacetylenic ring systems

Just, George; Singh, Rina

doi:10.1016/s0040-4039(00)96842-4

Cited by 47 publications

(15 citation statements)

References 9 publications

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“…Compound 10 was designed as a key intermediate to modify the B region meaningfully. The straightforward reaction sequence (Swern oxidation, 8 Grignard addition, Pd catalyzed coupling reaction, 9 hydrogenation and PDC oxidation) provided ketone 10 in 50% overall yield from 7. Treatment of 10 with semicarbazides or a hydrazine resulted in the formation of hydrazone, which on methyl ester hydrolysis gave the benzoic acid analogues 11, 12 and 13.…”

Section: Resultsmentioning

confidence: 99%

Discovery of Novel TRPV1 Ligands through Rational Approach Based on Its Putative Endogenous Ligand, 12(S)-HPETE

Min¹,

Lee²,

Kim³

et al. 2010

Bulletin of the Korean Chemical Society

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Section: Resultsmentioning

confidence: 99%

Discovery of Novel TRPV1 Ligands through Rational Approach Based on Its Putative Endogenous Ligand, 12(S)-HPETE

Min¹,

Lee²,

Kim³

et al. 2010

Bulletin of the Korean Chemical Society

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“…The crude product was purified by column chromatography (30% to 50% of ethyl acetate in hexanes to 30% of ethyl acetate in dichloromethane) yielding 2.82 g (quant.) of 15 as yellowish oil. 1 H NMR: 7.40–7.38 (dd, J 1 = 3.4 Hz, J 2 = 5.6 Hz, 2H), 7.25–7.23 (dd, J 1 = 3.4 Hz, J 2 = 5.6 Hz, 2H), 4.54 (s, 4H), 4.05 (br s, 2H).…”

Section: Methodsmentioning

confidence: 99%

Wolff rearrangement of β‐alkynyl‐α‐diazo‐β‐ketoesters: light‐induced acetylene–allene isomerization and its use for activation of enediynes

Zhegalova

Popik

2011

J of Physical Organic Chem

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Irradiation of β‐phenylethynyl‐α‐diazo‐β‐ketoester with 300 or 350 nm light results in efficient and regioselective Wolff rearrangement producing only the product of alkynyl group migration. Addition of alcohols to the resulting α‐oxoketene yields α‐phenylethynyl‐β‐diester, which undergoes rapid (τ < 1 min) tautomerization to 1,1‐dicarbalkoxyallene. The latter then adds second molecule of alcohol in Michael fashion to form the final product, 2‐(1‐alkoxy‐2‐phenylvinyl)malonic ester. α‐Phenylethynyl‐β‐ketoacid produced from the ketene in aqueous solutions does not isomerize to an allene but rather undergoes decarboxylation to give β,γ‐acetylenic ester. Introduction of o‐(3‐hydroxy‐1‐propynyl) fragment in the structure of the parent α‐diazo‐β‐ketoester allowed us to achieve two goals simultaneously: ring closure by intramolecular nucleophilic attack of propargyl alcohol on photo‐generated ketene and the subsequent acetylene–allene rearrangement. The resulting enyne–allene undergoes spontaneous Myers–Saito cycloaromatization generating 1,4‐biradical. In alcohol solutions, however, ketene reaction with solvent outcompetes the intramolecular process. Copyright © 2011 John Wiley & Sons, Ltd.

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“…16 This straightforward reaction furnished the tricyclic system 17 8 in 48% yield (Scheme 3). 16 This straightforward reaction furnished the tricyclic system 17 8 in 48% yield (Scheme 3).…”

Section: Methodsmentioning

confidence: 99%

Straightforward Access to [6]Metacyclophene-based Enynes by an Inter-Intramolecular Tandem Etherification through a One-Pot Double S_NAr Reaction

2000

Synlett

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The first application in the enediyne area of an inter-intramolecular tandem one-pot double S N Ar reaction is demonstrated towards the synthesis of new bi-and tricyclic enediynes 1 and 17, respectively. These polyunsaturated macrocycles are very stable and are not prone to rearrange to a diradical species via a Bergman cycloaromatization. The 1,3-substitution pattern on the aromatic ring could impede this thermal process from occurring.

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The synthesis of 11-13-membered diacetylenic and 18-membered tetraacetylenic ring systems

Cited by 47 publications

References 9 publications

Discovery of Novel TRPV1 Ligands through Rational Approach Based on Its Putative Endogenous Ligand, 12(S)-HPETE

Discovery of Novel TRPV1 Ligands through Rational Approach Based on Its Putative Endogenous Ligand, 12(S)-HPETE

Wolff rearrangement of β‐alkynyl‐α‐diazo‐β‐ketoesters: light‐induced acetylene–allene isomerization and its use for activation of enediynes

Straightforward Access to [6]Metacyclophene-based Enynes by an Inter-Intramolecular Tandem Etherification through a One-Pot Double S_NAr Reaction

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The synthesis of 11-13-membered diacetylenic and 18-membered tetraacetylenic ring systems

Cited by 47 publications

References 9 publications

Discovery of Novel TRPV1 Ligands through Rational Approach Based on Its Putative Endogenous Ligand, 12(S)-HPETE

Discovery of Novel TRPV1 Ligands through Rational Approach Based on Its Putative Endogenous Ligand, 12(S)-HPETE

Wolff rearrangement of β‐alkynyl‐α‐diazo‐β‐ketoesters: light‐induced acetylene–allene isomerization and its use for activation of enediynes

Straightforward Access to [6]Metacyclophene-based Enynes by an Inter-Intramolecular Tandem Etherification through a One-Pot Double SNAr Reaction

Contact Info

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Straightforward Access to [6]Metacyclophene-based Enynes by an Inter-Intramolecular Tandem Etherification through a One-Pot Double S_NAr Reaction