A Convenient Synthesis of Ethynyl-<i>N</i>-heteroarenes

Ames, D. E.; Bull, DJ; Takundwa, C. C.

doi:10.1055/s-1981-29448

Cited by 115 publications

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“…The palladium-catalyzed reaction of 2-bromopyridine with phenylacetylene was reported initially by Castro and Stephens (19) and later by Ames et al (20) to give excellent yields of 2-pyridylphenylacetylene. In addition, the reaction of 2-bromopyridine with 2-methylbut-3-yne-2-01 (20) and with trimethylsilylacetylene (21,22), respectively, has been reported, the products of each of these reactions being precursors to 2-ethynylpyridine.…”

Section: Introductionmentioning

confidence: 97%

“…In addition, the reaction of 2-bromopyridine with 2-methylbut-3-yne-2-01 (20) and with trimethylsilylacetylene (21,22), respectively, has been reported, the products of each of these reactions being precursors to 2-ethynylpyridine. In one of our synthetic projects in ligand design and synthesis we were interested in the synthesis of the hexadentate ligand 1.…”

Section: Introductionmentioning

confidence: 99%

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Bipyridylacetylenes 1: the synthesis of some bipyridylacetylenes via the palladium-catalyzed coupling of acetylenes with 2,2′-dibromobipyridyl, and the single crystal X-ray structure of 6,6′-bisphenylethynyl-2,2′-bipyridine

Butler¹,

Soucy-Breau²

1991

Can. J. Chem.

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. Can. J. Chem. 69, 11 17 (1991). The synthesis of a series of 6,6'-diethynyl-2,2'-bipyridyls from the palladium-catalyzed coupling of 6,6'-dibromo-2,2'-bipyridine with a series of arylacetylenes is reported. The single crystal X-ray structure of 6,6'-phenylethynyl-2,2'bip ridyl was determined. Crystal data: monoclinic, A2/a, with cell constants a = 10.0385(4), b = 9.2166(4), c = 21.4130(8) 2 and p = 102.981(3)"; DCaIc, = 1.226g ~m -~, Z = 4, Rf = 0.045, S = 1.22, using 886 reflections of the 1443 unique reflections.The packing diagram indicates essentially that the molecules pack in a layered assembly with the nitrogen atoms of the dipyridyl groups on opposite sides and with a dihedral angle of 59.85(16)" between the pyridyl and phenyl groups. The acetylenic bond distances are normal.Key words: acetylene, palladium, catalysis, coupling, monomers, crystal structure.IAN R. BUTLER et CHANTAL SOUCY-BREAU. Can. J. Chem. 69, 1117 (1991). Faisant appel un couplage catalysC par le palladium de la 6,6'-dibromo-2,2'-bipyridine avec une sCrie d'arylacCtylitnes, on a rkalisC la synthkse d'une sCrie de 6,6'-diCthyny1-2,2'-bipyridyles. On a dCterminC la structure cristalline du 6,6'-phCnylCthylny1-2,2'-bipyridyle par diffraction des rayons-X sur un cristal unique. Les cristaux sont monocliniques, groupe d'espace A2/a avec a = 10,0385(4), b = 9,2166 (4)

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Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Bipyridylacetylenes 1: the synthesis of some bipyridylacetylenes via the palladium-catalyzed coupling of acetylenes with 2,2′-dibromobipyridyl, and the single crystal X-ray structure of 6,6′-bisphenylethynyl-2,2′-bipyridine

Butler¹,

Soucy-Breau²

1991

Can. J. Chem.

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“…TMS-acetylene) which is unmasked via thermolysis in the presence of base with evolution of acetone. 19,20 It was in the context of the use of this reagent as a partner for Sonogashira coupling with 2-trifloxy-N-acetylaniline (1a) that we serendipitously discovered the facile cyclization process described herein. Thus, following Pd/Cu catalyzed coupling to yield alkynyl aniline 3a in 76% yield, attempted acid catalyzed hydrolysis of the acetamide by heating in c.HCl/water (1:1, v/v), was found to furnish dimethyl-2,3-dihydro-1H-quinolin-4-one (4a) in 98% yield after basic workup and chromatographic purification (Scheme 2).…”

mentioning

confidence: 95%

2-Substituted-2,3-dihydro-1H-quinolin-4-ones via Acid-Catalyzed Tandem Rupe Rearrangement-Donnelly-Farrell Ring Closure of 2-(3′-Hydroxypropynyl)anilines

Pisaneschi¹,

Sejberg²,

Blain³

et al. 2011

Synlett

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A range of 2-substituted 2,3-dihydro-1H-quinolin-4-ones have been synthesized from anilines by a two-step process involving Sonogashira coupling with a propargyl alcohol then acid catalyzed cyclization of the resulting 2-(3'-hydroxypropynyl)anilines. The cyclization reaction appears to proceed via regioselective rearrangement of the propargyl alcohol to an -unsaturated ketone (Rupe rearrangement) and then 6-endo-trig ring-closure (Donnelly-Farrell cyclisation). The isolation of the -unsaturated ketone intermediate in one example supports this pathway.

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“…In addition, a mode 7924 chromatatron supplied by Harrison Research was used with a silica gel support (Merck 7749-60 PF254 plates). Substituted acetylenes were prepared by palladium-catalysed coupling reactions of phenylacetylene and the appropriate aryl halide (7). Derivatives of dicarbonyl(T5-cyclopentadienyl)iron, (Fp), were prepared either by reaction of sodium dicarbonyl(T5-cyclopentadienyl) ferrate with the appropriate aroyl halide (a), or by reaction of dicarbonyl(-r15-cyclopentadienyl)iron iodide with the appropriate aryllithium (9).…”

Section: Methodsmentioning

confidence: 99%

“…For personal use only. 7.69 (dd, I, JH-H = 1.1, 4.9); 7.77 (dd, I, J H P H = 1.1, 3.9). 17b: 6.93 (dd, 1, JHPH = 4.9, 3.9); 7.16-7.58 (rn's, 12, including dd at 7.51, JHAH = 4.9, 1.2, and dd at 7.56, JH-H = 3.9, 1.2).…”

Section: Reaction Of Fp-2-thienoyl With Diphenylacetylenementioning

confidence: 99%

The reaction of (η⁵-cyclopentadienyl)dicarbonyliron(2-thienoyl) with acetylenes; a mechanistic study using proton nuclear magnetic resonance, and application in synthesis

Butler¹

1990

Can. J. Chem.

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IAN R. BUTLER. Can. J. Chem. 68, 1979Chem. 68, (1990. The thermal reactions of dicarbonyl-r15-cyclopentadienyl(2-thienoyl)iron with a series of substituted acetylenes to give indenones and cyclopentathiophenones have been reinvestigated. The results obtained support a reaction mechanism involving initial acetylene insertion followed by that of carbon monoxide, in contradiction to the previously reported results. 'The reaction products were identified and characterized primarily using 2D 'H nmr spectroscopy.Key words: acetylene, carbon monoxide, iron, indenone, mechanism, thienyl.IAN R. BUTLER. Can. J. Chem. 68, 1979Chem. 68, (1990 On a rketudik les rkactions thermiques du dicarbonyl-r15-cyclopentadi~nyl(2-thienoyl)fer avec une skrie d'acktylknes substitukes qui conduisent ?i des indknones et ?i des cyclopentathiophtnones. Les rtsultats obtenus sont en accord avec un mkcanisme rkactionnel impliquant une insertion initiale de l'acetylkne, suivie de celle du monoxyde de carbone; ce mCcanisme est en contradiction avec les rksultats rapportks antkrieurement. Pour identifier et pour caracttriser les produits rkactionnels, on a principalement fait appel ?i la spectroscopic rmn du 'H en 2D.Mots clPs: acttylkne, monoxyde de carbone, fer, indtnone, mkcanisme, thienyle.[Traduit par la revue] IntroductionThe insertion of acetylenes into metal-carbon bonds is a synthetically useful procedure, although the mechanistic details of such processes are not fully understood. Recently we have elucidated some of the mechanistic features of one specific type of reaction in this class, namely that of the thermal reaction of dicarbonyl-q5-cyclopentadienyliron(I)aryls, FPAr, with diarylacetylenes to give [lw-2,3-diarylinden-1-ones, using deuterium labelled samples (1). A summary of the proposed mechanistic results is shown in Scheme 1, for the reaction of Fp(pheny1-d5) with diphenylacetylene. In addition to the indenone products, ferrocene and mono and l,lf-bis(pheny1-d5) ferrocene are observed as by-products, indicating the transfer of the a bound phenyl group to the q5-cyclopentadienyl ring. By studying the reactions (photochemical and thermal) of the related Fp(1-and 2-naphthoyl) compounds with diphenylacetylene, we were able to show that the insertion of the diarylacetylene precedes that of carbon monoxide, Scheme 2 (2). Moreover, by independent synthesis of the proposed intermediate, 4 (undeuterated) in Scheme 1, we were able to show that such compounds decompose cleanly to [ l HI-2,3-diphenylinden-1-one (3).

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A Convenient Synthesis of Ethynyl-N-heteroarenes

Cited by 115 publications

References 0 publications

Bipyridylacetylenes 1: the synthesis of some bipyridylacetylenes via the palladium-catalyzed coupling of acetylenes with 2,2′-dibromobipyridyl, and the single crystal X-ray structure of 6,6′-bisphenylethynyl-2,2′-bipyridine

Bipyridylacetylenes 1: the synthesis of some bipyridylacetylenes via the palladium-catalyzed coupling of acetylenes with 2,2′-dibromobipyridyl, and the single crystal X-ray structure of 6,6′-bisphenylethynyl-2,2′-bipyridine

2-Substituted-2,3-dihydro-1H-quinolin-4-ones via Acid-Catalyzed Tandem Rupe Rearrangement-Donnelly-Farrell Ring Closure of 2-(3′-Hydroxypropynyl)anilines

The reaction of (η⁵-cyclopentadienyl)dicarbonyliron(2-thienoyl) with acetylenes; a mechanistic study using proton nuclear magnetic resonance, and application in synthesis

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A Convenient Synthesis of Ethynyl-N-heteroarenes

Cited by 115 publications

References 0 publications

Bipyridylacetylenes 1: the synthesis of some bipyridylacetylenes via the palladium-catalyzed coupling of acetylenes with 2,2′-dibromobipyridyl, and the single crystal X-ray structure of 6,6′-bisphenylethynyl-2,2′-bipyridine

Bipyridylacetylenes 1: the synthesis of some bipyridylacetylenes via the palladium-catalyzed coupling of acetylenes with 2,2′-dibromobipyridyl, and the single crystal X-ray structure of 6,6′-bisphenylethynyl-2,2′-bipyridine

2-Substituted-2,3-dihydro-1H-quinolin-4-ones via Acid-Catalyzed Tandem Rupe Rearrangement-Donnelly-Farrell Ring Closure of 2-(3′-Hydroxy­propynyl)anilines

The reaction of (η5-cyclopentadienyl)dicarbonyliron(2-thienoyl) with acetylenes; a mechanistic study using proton nuclear magnetic resonance, and application in synthesis

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2-Substituted-2,3-dihydro-1H-quinolin-4-ones via Acid-Catalyzed Tandem Rupe Rearrangement-Donnelly-Farrell Ring Closure of 2-(3′-Hydroxypropynyl)anilines

The reaction of (η⁵-cyclopentadienyl)dicarbonyliron(2-thienoyl) with acetylenes; a mechanistic study using proton nuclear magnetic resonance, and application in synthesis