128351-01-9

Upstream product

• 13146-23-1 copper(I) phenylacetylenide 
• 75833-63-5 2-iodo-1-methyl-1H-indole 
• 536-74-3 phenylacetylene 
• 603-76-9 1-methylindole 
• 28995-88-2 1-methyl-4-((phenylethynyl)sulfonyl)benzene 
• 74-88-4 methyl iodide 
• 1043252-30-7 2-[(4-phenyl)buta-1,3-diyn-1-yl]aniline 
• 552-89-6 2-nitro-benzaldehyde 
• 167558-54-5 2-(2,2-dibromo-vinyl)-phenylamine 
• 923270-57-9 2-methylaminophenylacetylene 
• 170956-92-0 N-methyl-2-(2-phenylethynyl)aniline 
• 591-50-4 iodobenzene 
• 85094-87-7 1-methyl-2-ethynylindole 
• 27421-51-8 1-methyl-1H-indole-2-carboxaldehyde 

Downstream Products

• 95104-18-0 2-phenyl-9-methyl-γ-carboline N-oxide 
• 95104-16-8 3-formyl-2-phenylethynyl-1-methylindole oxime 
• 1262153-71-8 C₃₀H₂₇NO₄ 
• 95104-17-9 1-methyl-2-(2-phenylethynyl)-1H-indole-3-carbaldehyde 

Relevant academic research and scientific papers

Direct construction of fused indoles by gold-catalyzed cascade cyclization of conjugated diynes

A gold-catalyzed cascade cyclization of aniline derivatives bearing a conjugated diyne moiety was developed. Following the 5-endo-dig indole formation, subsequent 7-endo-dig cyclization predominated over 6-exo-dig cyclization to give the indole fused with a seven-membered ring in good yields.

Synthesis of annulated bis-indoles through Au(i)/Br?nsted acid-catalyzed reactions of (1H-indol-3-yl)(aryl)methanols with 2-(arylethynyl)-1H-indoles

A general method to access annulated bis-indoles from (1H-indol-3-yl)(aryl)methanols and 2-(arylethynyl)-1H-indoles under the catalysis of the Ph3PAuOTf/Br?nsted acid binary catalyst system has been developed. The reaction was found to proceed in a highly efficient manner and benefit from easy-to-make starting materials, broad substrate scope and operational simplicity. The potential of this method has also been exemplified for the synthesis of pyrrole-annulated indoles using 2-(phenylethynyl)-1H-indoles and phenyl(1H-pyrrol-2-yl)methanols. Furthermore, the use of a ternary catalyst system, involving PdCl2/Br?nsted acid/Ph3PAuOTf catalysts, has been realized for the synthesis of annulated bis-indoles starting directly from 2-(phenylbuta-1,3-diyn-1-yl)aniline and (1H-indol-3-yl)(aryl)methanol. Mechanistically, this reaction is very interesting since the overall process involves three different catalytic cycles catalyzed by three different catalysts in a relay fashion.

Efficient synthesis of pyrano[4,3-b]indol-1(5H)-ones from CO2 and alkynyl indoles promoted by a protic ionic liquid

An efficient method was developed for the synthesis of pyrano[4,3-b]indol-1(5H)-ones, which uses a protic ionic liquid [HTBD+][TFE–] as both the solvent and reaction promoter. The reactions could be efficiently carried out at atmosph

Arylsulfonylacetylenes as alkynylating reagents

The unexpected anti-Michael addition of RLi to β-substituted sulfonylacetylenes, followed by in situ elimination of the ion sulfinate, allows the alkynylation of C(sp2) and C(sp3). Aryl and heteroaryl acetylenes, enynes, and mono and dialkyl alkynes can be obtained in very high yields under very mild conditions, avoiding the use of transition metals as catalysts and, in many cases, haloderivatives as starting materials. Furthermore, the use of lithium 2-p-tolylsulfinyl benzylcarbanions as nucleophiles of these reactions allows their stereocontrolled alkynylation, affording enantiomerically pure alkynes or enantioenriched allenes depending on the protonating agent (NH4Cl or H2O).

Arylsulfonylacetylenes as alkynylating reagents of C sp 2 -H bonds activated with lithium bases

Chameleon: A new strategy for the synthesis of a wide variety of alkynyl derivatives by the reaction of substituted arylsulfonylacetylenes with organolithium species is described (see scheme). The high yields, the simplicity of the experimental procedure, the broad scope of this reaction, and the formation of Csp-C sp 2 bonds without using transition metals are the main features of this methodology. Copyright

Expanding the scope of arylsulfonylacetylenes as alkynylating reagents and mechanistic insights in the formation of Csp2-Csp and Csp 3-Csp bonds from organolithiums

We describe the unexpected behavior of the arylsulfonylacetylenes, which suffer an "anti-Michael" addition of organolithiums producing their alkynylation under very mild conditions. The broad scope, excellent yields, and simplicity of the experimental procedure are the main features of this methodology. A rational explanation of all these results can be achieved by theoretical calculations, which suggest that the association of the organolithiums to the electrophile is a previous step of their intramolecular attack and is responsible for the unexpected "anti-Michael" reactions observed for substituted sulfonylacetylenes. A calculated conclusion: A new transition-metal-free strategy for the synthesis of any kind of alkynyl derivatives in high yields in the reaction of organolithium species with arylsulfonylacetylenes is presented (see scheme). Theoretical calculations provide a rational explanation and suggest that association of the organolithium to the electrophile is a previous step of their intramolecular attack and is responsible for the "anti-Michael" reaction. Copyright

Regiochemistry in cobalt-mediated intermolecular Pauson-Khand reactions of unsymmetrical internal heteroaromatic alkynes with norbornene

The intermolecular Pauson-Khand (PK) reactions of sterically comparable (2-phenylethynyl)heteroaromatic compounds with norbornene, mediated by Co 2(CO)8 to give cyclopentenone products, were examined in this study. A synthetic protocol utilizing focused-microwave dielectric heating proved indispensable in the efficient synthesis of the PK cyclopentenone products. "π-Deficient" heteroaromatic substrates, e.g., 2-pyrones, and some "π-excessive" heteroaromatics such as 2- and 3-thiophene and 2-furan favor the β-position in the newly formed cyclopentenone ring. Other π-excessive heteroaromatics such as 2-pyrrole or 2-indole favor the α-position. A π-excessive 3-indole derivative gave a nearly equal mixture of regioisomers. The position of the nitrogen in pyridyl-containing alkyne substrates also affects the regiochemical outcome of the PK reaction. A 2-pyridyl alkyne, possessing a proximal nitrogen, influences the regioselectivity relative to a 4-pyridyl variant quite dramatically, favoring the β-position in the newly formed cyclopentenone ring. A 2-pyrimidylalkyne exhibits similar behavior to the 2-pyridylalkyne. Compounds that do not participate in PK reactions with norbornene include (2-phenylethynyl)imidazoles and the related benzimidazoles, which promote rapid decomposition of the in situ generated (μ2-alkyne)Co2(CO)6 complexes. This stands in contrast with other nitrogen-containing heteroaromatics, e.g., pyrrole-, indole-, and pyrimidine-derived compounds, which effectively undergo PK reactions. Overall, the type of heteroaromatic group dramatically influences PK regioselectivity, which can in part be explained by rationalization of the current reaction mechanism, but not fully.

Tandem cyclopropane ring-opening/conia-ene reactions of 2-alkynyl indoles: A [3 + 3] annulative route to tetrahydrocarbazoles

A Zn(NTf2)2 catalyzed tandem reaction consisting of a nucelophilic ring opening of 1,1-cyclopropanediesters by 2-alkynyl indoles followed by a Conia-ene ring closure results in the efficient one-step synthesis of tetrahydrocarbazoles

SYNTHESIS AND CERTAIN PROPERTIES OF ACETYLENYLINDOLES

A group of new acetylenic derivatives of indole was synthesized by condensation of 2- and 3-iodoindoles with terminal acetylenes. 3-Iodoindole unsubstituted at the heteroatom is distinguished by an increased tendency to undergo deiodination under the reac