115085-22-8

Upstream product

• 17689-03-1 1-hexynyllithium 
• 104-87-0 4-methyl-benzaldehyde 
• 627-19-0 1-Pentyne 
• 3844-94-8 1-(trimethylsilyl)-1-hexyne 
• 218793-76-1 triethoxy(hex-1-yn-1-yl)silane 
• 693-02-7 hex-1-yne 
• 116-11-0 2-Methoxypropene 

Downstream Products

• 132454-06-9 1-[1-(2-Bromo-1-methoxy-cyclohexyloxy)-hept-2-ynyl]-4-methyl-benzene 
• 142641-81-4 (E)-1-(p-tolyl)-2-hepten-1-one 
• 142641-82-5 1-(p-tolyl)-3-hepten-1-one 
• 115085-28-4 1-[1-(2-Bromo-1-ethoxy-ethoxy)-hept-2-ynyl]-4-methyl-benzene 
• 1041850-09-2 2-methyl-4-(4'-methylphenyl)-5-n-pentylfuran-3-carboxylic acid ethyl ester 
• 1041850-01-4 3-acetyl-2-methylfuran-4-(4'-methylphenyl)-5-n-pentylfuran 
• 1092455-52-1 C₂₅H₃₆O₂ 
• 1042702-08-8 1,3-diphenyl-2-(1-p-tolylhept-2-ynyl)propane-1,3-dione 
• 1042702-06-6 C₁₉H₂₄O₂ 
• 1160492-95-4 (E)-1-chloro-1-phenyl-3-(p-tolyl)non-1-en-4-yne 
• 1139686-60-4 1-(3-chlorohepta-1,2-dienyl)-4-methyl-benzene 
• 1139686-76-2 1-(3-bromohepta-1,2-dienyl)-4-methyl-benzene 
• 1238187-45-5 5-butyl-2-(phenylsulfonyl)-3-p-tolyl-2,3-dihydroisoxazole 
• 1374748-15-8 1,2,3,4,5-pentafluoro-6-{1-(4-methylphenyl)hepta-1,2-dien-3-yl}benzene 

Relevant academic research and scientific papers

Gold(I)-Catalyzed Synthesis of Tetrahydrocarbazoles via Cascade [3,3]-Propargylic Rearrangement/[4+2] Cycloaddition of Vinylindoles and Propargylic Esters

A gold(I)-catalyzed cascade [3,3]-propargylic rearrangement and [4+2] cycloaddition reaction of 2-vinylindoles with propargylic esters is reported. The reaction leads to the synthesis of highly substituted tetrahydrocarbazole derivatives in high yields and diasteroselectivities. Furthermore, a preliminary screening for an asymmetric version of this reaction is described.

Vanadium(V)-mediated rearrangement/halogenation cascade: Synthesis of α-haloenones from propargyl alcohols

A method is described for the oxidative Meyer–Schuster-type rearrangement of propargylic alcohols to (Z)-α-chloro- and α-iodoenones using VOCl3 as a multifunctional reagent. The vanadium reagent is found to serve as rearrangement promoter as well as an active chlorenium ion donor. Yields are improved when VOCl3 is employed in conjunction with N-halosuccinimide reagents, giving some insights into the complex mechanism.

Synthesis of Vinyl-, Allyl-, and 2-Boryl Allylboronates via a Highly Selective Copper-Catalyzed Borylation of Propargylic Alcohols

An efficient methodology for the synthesis of vinyl-, allyl-, and (E)-2-boryl allylboronates from propargylic alcohols via Cu-catalyzed borylation under mild conditions is reported. In the presence of commercially available Cu(OAc)2 or Cu(acac)2 and Xantphos, the reaction affords the desired products in up to 92% yield with a broad substrate scope (43 examples). Isolation of an allenyl boronate as the reaction intermediate suggests that an insertion-elimination-type reaction, followed by borylcupration, is involved in the borylation of propargylic alcohols.

Dehydrogenative Meyer-Schuster-like rearrangement: A gold-catalyzed reaction generating an alkyne

Easily accessible propargylic esters are converted to the inverted alkynyl ketones in an oxidative gold-catalyzed reaction. Gagosz's catalyst in combination with PhI(OAc)2 is the best system for this conversion and 18 examples with yields up to 80 % are reported. The results indicate that the triple bond in the product is formed by elimination from a vinylgold intermediate. In a formal sense the new conversion overall is a dehydrogenative Meyer-Schuster rearrangement. It takes alkynes: Propargyl esters can be converted into alkynyl ketones by a new oxidative gold-catalyzed reaction. The best catalyst system is Ph3PAuCl/AgNTf2 in combination with the oxidant PhI(OAc)2. The yields are as high as 80 % and the reaction can be conducted in the presence of air. Copyright

Silver-catalyzed efficient synthesis of vinylene carbonate derivatives from carbon dioxide

It was found that the silver salt and base was an efficient catalytic system for the reaction of the secondary propargylic alcohol with carbon dioxide to afford various corresponding vinylene carbonate derivatives in good to high yields under mild conditions. Georg Thieme Verlag Stuttgart New York.

Highly diastereoselective synthesis of cyclopentenones via a one-pot gold catalysis, Nazarov cyclization and alkylation cascade

Starting from readily available propargylic carboxylates, three sequential transformations [gold-catalyzed tandem reaction, scandium(III) trifluoromethanesulfonate catalyzed Nazarov cyclization, alkylation reaction] in a one-pot process led to the formation of cyclopentenone derivatives in excellent diastereoselectivities and moderate to good overall yields. Georg Thieme Verlag Stuttgart. New York.

Catalytic asymmetric enyne addition to aldehdyes and Rh(I)-catalyzed stereoselective domino Pauson-Khand/[4 + 2] cycloaddition

The 1,1′-bi-2-naphthol-ZnEt2-Ti(OiPr) 4-Cy2NH system is found to catalyze the 1,3-enyne addition to aliphatic aldehydes as well as other aldehydes at room temperature with 75-96% yield and 82-97% ee. This system is also broadly applicable for the highly enantioselective reaction of other alkyl-, aryl-, and silylalkynes with structurally diverse aldehydes. The propargylic alcohols prepared from the catalytic asymmetric enyne addition to aliphatic aldehydes are used to prepare a series of optically active trienynes. In the presence of a catalytic amount of [RhCl(CO)2]2 and 1 atm of CO, the optically active trienynes undergo highly stereoselective domino Pauson-Khand/[4 + 2] cycloaddition to generate optically active multicyclic products. The Rh(I) catalyst is also found to catalyze the coupling of a diyne with CO followed by [4 + 2] cycloaddition to generate an optically active multicyclic product. These transformations are potentially useful for the asymmetric synthesis of polyquinanes containing a quaternary chiral carbon center.

Condensation of propargylic alcohols with N-methylcarbazole and carbazole in [bmim]PF6 ionic liquid; Synthesis of novel dipropargylic carbazoles using TfOH or Bi(NO3)3·5H2O as catalyst

A series of doubly-propargylated N-methylcarbazole and carbazole derivatives were synthesized in good to excellent isolated yields in (bmim)PF6 using triflic acid (10 mol %). The use of bismuth nitrate (20 mol %) instead of triflic acid allowed stepwise propargylation employing two different propargylic alcohols, to prepare mixed bis-propargylated carbazoles. Simple product isolation, mild reaction conditions, and repeated recycling and reuse of (bmim)PF6 are added advantages of this IL-mediated synthetic method.

Gold- and silver-catalyzed reactions of propargylic alcohols in the presence of protic additives

A wide range of primary, secondary and tertiary propargylic alcohols undergo a Meyer-Schuster rearrangement to give enones at room temperature in the presence of a gold(I) catalyst and small quantities of MeOH or 4-methoxyphenylboronic acid. The syntheses of the enone natural products isoegomaketone and daphenone were achieved using this reaction as the key step. The rearrangement of primary propargylic alcohols can readily be combined in a one-pot procedure with the addition of a nucleophile to the resulting terminal enone, to give β-aryl, β-alkoxy, β-amino or β-sulfido ketones. Propargylic alcohols bearing an adjacent electron-rich aryl group can also undergo silver-catalyzed substitution of the alcohol with oxygen, nitrogen and carbon nucleophiles. This latter reaction was initially observed with a batch of gold catalyst that was probably contaminated with small quantities of silver salt.

A concise access to (polyfluoroaryl)allenes by Cu-catalyzed direct coupling with propargyl phosphates

A copper-based catalyst system for the direct coupling of polyfluoroarenes with propargyl phosphates has been developed. The catalysis can provide a rapid and concise access to (polyfluoroaryl)allenes, which can be important building blocks for the synthesis of fluorinated functional materials.