1002-28-4Relevant academic research and scientific papers
A convenient high-yield procedure for the β-hydroxyethylation of acetylenes with epoxyethane in liquid ammonia
Verkruijsse,Brandsma
, p. 235 - 237 (1991)
3-Butyn-1-ol and homologues, RC≡CCH2CH2OH (R = H or alkyl), have been obtained in excellent yields from alkynyllithium derivatives, RC≡CLi, and epoxyethane in liquid ammonia.
Antifungal properties of 3-n-alkyn-1-ols and synergism with 2-n-alkyn-1-ols and ketoconazole
Gershon,Jerome,McElwain
, p. 556 - 558 (1985)
Twelve 3-n-alkyn-1-ols (C4-C12, C14, C16, and C18) were tested against Aspergillus oryzae, Aspergillus niger, Trichoderma viride, and Myrothecium verrucaria in Sabouraud dextrose agar at pH 5.6 and 7.0. Toxicity to Candida albicans, Candida tropicalis, Trichophyton mentagrophytes, and Mucor mucedo was determined in the same medium at pH 5.6 and 7.0 in the absence and presence of 10% beef serum. Fungitoxicity was strongly influenced by chain length, slightly by pH of the medium, and significantly but not strongly by the presence of beef serum. 3-n-Decyn-1-ol, 3-n-undecyn-1-ol, and 3-n-dodecyn-1-ol were the most active members of the series. Synergism toward C. albicans and C. tropicalis was observed between 3-n-undecyn-1-ol and ketoconazole, and a mixture of 3-n-undecyn-1-ol, 2-n-undecyn-1-ol, and ketoconazole in Sabouraud dextrose agar at pH 7.0 in the presence of 10% human serum.
Atom-Economical Cross-Coupling of Internal and Terminal Alkynes to Access 1,3-Enynes
Liu, Mingyu,Tang, Tianhua,Apolinar, Omar,Matsuura, Rei,Busacca, Carl A.,Qu, Bo,Fandrick, Daniel R.,Zatolochnaya, Olga V.,Senanayake, Chris H.,Song, Jinhua J.,Engle, Keary M.
supporting information, p. 3881 - 3888 (2021/04/06)
Selective carbon-carbon (C-C) bond formation in chemical synthesis generally requires prefunctionalized building blocks. However, the requisite prefunctionalization steps undermine the overall efficiency of synthetic sequences that rely on such reactions, which is particularly problematic in large-scale applications, such as in the commercial production of pharmaceuticals. Herein, we describe a selective and catalytic method for synthesizing 1,3-enynes without prefunctionalized building blocks. In this transformation several classes of unactivated internal acceptor alkynes can be coupled with terminal donor alkynes to deliver 1,3-enynes in a highly regio- and stereoselective manner. The scope of compatible acceptor alkynes includes propargyl alcohols, (homo)propargyl amine derivatives, and (homo)propargyl carboxamides. This method is facilitated by a tailored P,N-ligand that enables regioselective addition and suppresses secondary E/Z-isomerization of the product. The reaction is scalable and can operate effectively with as low as 0.5 mol % catalyst loading. The products are versatile intermediates that can participate in various downstream transformations. We also present preliminary mechanistic experiments that are consistent with a redox-neutral Pd(II) catalytic cycle.
Synthesis of substituted α-methylene-γ-butyrolactones from chloroformates via palladium catalysed cyclisation-anion capture
Grigg,Savic
, p. 2381 - 2382 (2007/10/03)
Cyclisation of chloroformates onto proximate alkyne functionality in the presence of a Pd(0) catalyst followed by anion capture affords α-methylene-γ-butyrolactone derivatives in moderate to good yields.
A new, highly stereoselective approach to pyrrolidines via overall 5-endo-trig cyclisations of homoallylic tosylamides
Jones, Andrew D.,Knight, David W.
, p. 915 - 916 (2007/10/03)
Iodocyclisations of E-homoallylic tosylamides 7 lead to excellent yields of either 2,5-trans- or 2,5-cis-3-iodopyrrolidines (10 or 11), depending upon the reaction conditions.
Acetylenes as Potential Antarafacial Components in Concerted Reactions. Formation of Pyrroles from Thermolyses of Propargylamines, of a Dihydrofuran from a Propargylic Ether, and of an Ethylidenepyrrolidine from a β-Amino Acetylene
Viola, Alfred,Collins, John J.,Filipp, Nicholas,Locke, John S.
, p. 5067 - 5075 (2007/10/02)
A thermal cyclization of acetylenic compounds provides evidence for the ability of acetylenic links to act as antarafacial components in processes.The cyclization competes with the normally favored acetylenic retro-ene reaction.Propargylic amines, without substituents whose presence would hinder a tight cyclic transition state, yield intermediate pyrrolines whose subsequent hydrogen elimination affords pyrroles in small amounts.The same process in 2-ethynyltetrahydropyran affords 8-oxabicyclooctane in 35percent yield.A related thermal reaction of N-methyl-3-hexyn-1-amine provides a quantitative transformation to N-methyl-2-ethylidenepyrrolidine in a nominal s + 2a + 2s + 2s> Moebius process, wherein the acetylenic unit is the antarafacial component.Evidence for concertedness in these reactions is discussed.
Syntheses of Monounsaturated Sex Pheromones of Lepidoptera via 3-Alkyn-1-ols
Pop, Lidia,Oprean, I.,Barabas, A.,Hodosan, F.
, p. 867 - 878 (2007/10/02)
3-Alkyn-1-ols as intermediate synthons in the preparation of some Lepidoteran sex pheromones were utilized.Characteristic fragmentations reflecting the position of the triple bond were found in the mass spectra of 3-alkyn-1-ols and alkyn-1-yl acetates in contrast to 1-tert-butoxy-alkynes.A partial isomerization of 1-tosyloxy-3-(Z)-octene to 1-bromo-3-(E)-octene within the reaction with NaBr in DMF was noticed by GC and 13C-n.m.r., for which a mechanism involving homoconjugation in an intermediate non-classical carbonium ion was suggested.
