216306-60-4

Upstream product

• 536-74-3 phenylacetylene 
• 6738-06-3 phenylethynylmagnesium bromide 
• 38846-64-9 2-ethynylbenzaldehyde 
• 591-50-4 iodobenzene 
• 59046-72-9 o-(phenylethynyl)benzaldehyde 
• 26260-02-6 2-iodobenzaldehyde 
• 6630-33-7 ortho-bromobenzaldehyde 

Downstream Products

• 1280219-92-2 phenyl(10-phenylphenanthren-4-yl)methanone 
• 1280219-89-7 (Z)-4-(3-phenyl-1-(phenylethynyl)naphthalen-2-yl)but-3-en-2-one 
• 1280219-91-1 2-methyl-5-(3-phenyl-1-(2-(phenylethynyl)phenyl)prop-2-ynyl)furan 
• 1280219-90-0 (3-methyl-10-phenylphenanthren-4-yl)(phenyl)methanone 
• 1370697-43-0 1,3-diiodo-2-phenylnaphthalene 
• 1394324-93-6 (Z)-1-benzylidene-3-(phenylethynyl)-1,3-dihydroisobenzofuran 
• 1394324-92-5 phenyl(2-phenyl-3-(tributylstannyl)naphthalen-1-yl)methanone 

Relevant academic research and scientific papers

Br?nsted/Lewis Acid-Promoted Site-Selective Intramolecular Cycloisomerizations of Aryl-Fused 1,6-Diyn-3-ones for Diversity-Oriented Synthesis of Benzo-Fused Fluorenes and Fluorenones and Naphthyl Ketones

Herein, a facile diversity-oriented approach to access functionalized benzo[a]fluorenes, benzo[b]fluorenones, and naphthyl ketones has been demonstrated via site-selective intramolecular cyclization of aryl-fused 1,6-diyn-3-ones. Synthesis of benzo[a]fluorenes and naphthyl ketones has been achieved selectively using TfOH and AgBF4, respectively, via in situ-formed acetals. Aryl-fused 1,6-diyn-3-ones undergo triflic acid-mediated intramolecular cyclization, leading to benzo[b]fluorenone derivatives via a radical intermediate as supported by EPR studies. Kinetic studies of these transformations have also been performed by UV-visible spectroscopic analysis to shed light on the reaction profile.

Catch-Release System for Dosing and Recycling Silver(I) Catalyst with Status of Catalytic Activity Reported by Fluorescence

The silver(I) catch-release system composed of nanoswitch 1 and the anthracene-appended crown ether 2 is infallibly driven by chemical triggers and ion transfer. Any state of the silver(I) translocation is self-reported by a ratiometric emission signature at 472 and 554 nm. In the self-sorted networked state I, the silver(I) ions are tightly shielded inside nanoswitch [Ag(1)]+ ("catch") so that their catalytic activity is zero while emission at 554 nm is maximum. Addition of zinc(II) releases silver(I) from [Ag(1)]+ and generates the catalytically active and fluorescent complex [Ag(2)]+. In this networked state II ("release") both catalytic activity and emission at 472 nm are maximum. Removal of the original trigger regenerates networked state I. ON/OFF control and recycling of catalyst was demonstrated over three in situ cycles.

Cobalt-catalyzed regioselective syntheses of indeno[2,1-: C] pyridines from nitriles and diynes bearing propargyl fragments

A highly efficient CoI2/o-phenanthroline catalyzed cycloaddition reaction of diynes bearing TBS protected propargylic alcohol fragments with nitriles has been developed. This methodology offers regioselective access, with good functional group tolerance, to various indeno[2,1-c]pyridine derivatives in moderate to excellent yields. It was found that o-phenanthroline as a bidentate nitrogen ligand showed high efficacy in this cycloaddition reaction.

Gold-Catalyzed Oxidative Cyclizations of { o-(Alkynyl)phenyl propargyl} Silyl Ether Derivatives Involving 1,2-Enynyl Migration: Synthesis of Functionalized 1 H-Isochromenes and 2 H-Pyrans

A new and convenient strategy for the synthesis of functionalized 1H-isochromene and 2H-pyran derivatives based on gold-catalyzed oxidative cyclizations of o-(alkynyl)phenyl propargyl ether derivatives has been developed. The reaction proceeds via gold-catalyzed highly regioselective oxidation, followed by 1,2-migration of an enynyl group and nucleophlic addition. Isocoumarins were also constructed through oxidative cleavage of the exocyclic double bond of the obtained 1H-isochromenes.

Base-Catalyzed Cyclization of 1,6-Diynyl Carboxylates Involving Propargyl-Allenyl Isomerization: Efficient Synthesis of Benzo[b]fluorene and Its Analogues

An efficient protocol for the synthesis of benzo[b]fluorenes via base-catalyzed cyclization of 1,6-diynyl carbonates, esters or ethers has been developed. The reaction likely proceeds via base-induced propargyl-allenyl isomerization followed by Schmittel-type cyclization. Heterocycle-fused fluorenes such as thiophene- or pyridine-fused substrates could also be conveniently constructed by this method. The synthetic utility of this reaction was demonstrated by the preparation of up to seven-ring fused polycyclic aromatic hydrocarbons. (Figure presented.).

Domino Fragmentations in Traceless Directing Groups of Radical Cascades: Evidence for the Formation of Alkoxy Radicals via C-O Scission

Direct evidence for the formation of alkoxy radicals is reported in radical cascades using traceless directing groups. Despite the possibility of hydrogen abstraction in the fragmenting step, followed by loss of R-OH, β-scission is preferred for the formation of alkoxy radicals. For the first time, the C-O radical was intermolecularly trapped using a silyl enol ether. Various C-X fragmenting groups were explored as possible traceless directing groups for the preparation of extended polyaromatics. Computational evidence shows that a combination of aromatization, steric and stereoelectronic effects assists the fragmentation to alkoxy radicals. Additionally, a new through-space interaction was discovered between O and Sn in the fragmentation as a specific transition state stabilizing effect.

A [2+2+2]-Cyclotrimerization Approach to Selectively Substituted Fluorenes and Fluorenols, and Their Conversion to 9,9′-Spirobifluorenes

Synthesis of selectively substituted fluorenes and fluorenols was achieved by using catalytic [2+2+2]cyclotrimerization. Various starting diynes were reacted with different alkynes in the presence of a catalytic amount of Wilkinson's catalyst (RhCl(PPh3)3) providing the compounds possessing the fluorene scaffold in good isolated yields. A set of four regioselectively substituted fluorenols was converted to the corresponding 9,9′-spirobifluorenes and their spectral characteristics were measured. A select group! Selectively substituted fluorenes and fluorenols were synthesized by RhCl(PPh3)3 catalyzed [2+2+2]-cyclotrimerization of the diynes with alkynes. Fluorenols were subsequently transformed into a set of four regioselectively substituted 9,9′-spirobifluorenes.

Exo-dig radical cascades of skipped enediynes: Building a naphthalene moiety within a polycyclic framework

Cascade radical transformations of acyclic precursors open efficient, convenient and atom-economical access to functionalized compounds of increased structural complexity. This report describes a selective sequence of 5-exo-dig and 6-exo-dig cyclizations followed by attack at a pendant aromatic moiety and rearomatization.

Platinum-catalyzed tandem cycloisomerization reaction of benzoendiynyl esters: Regioselective long-range 1,5-Acyl migration

A PtII-catalyzed intramolecular chemo- and regioselective pentannulation/long-range 1,5-acyl migration reaction is described. This cascade cycloisomerization protocol produces a wide variety of benzofulvene diketones in good to excellent yields with exclusively the Z configuration of the exocyclic double bond of the final product. The 18O isotope experiment together with 13C NMR, HRMS, and HMBC analyses confirmed an interesting long-range acyl rearrangement process in this transformation.

Sequential [3+2] cycloaddition/air oxidation reactions: Triazoloyl ion assisted oxidative cleavage of alkynes

Upon treatment with sodium azide in DMF, bisalkynes undergo chemoselective [3+2] cycloaddition followed by oxidative cleavage of the other alkyne unit by atmospheric oxygen. The neighboring triazoloyl ion is found to assist the cleavage process ultimately to deliver an acid and an aldehyde. Cycloaddition of azide with a bisalkyne chemoselectively forms a triazole, which subsequently undergoes oxidative cleavage by atmospheric oxygen to yield a carboxylic acid and an aldehyde. The mechanism for this reaction is investigated in depth. Copyright