2243-98-3Relevant academic research and scientific papers
Generation of Akylidenecarbenes by the Alkenation of Carbonyl Compounds with Lithiotrimethylsilyldiazomethane
Ohira, Susumu,Okai, Keiji,Moritani, Takanori
, p. 721 - 722 (1992)
The reaction of carbonyl compounds and lithiotrimethylsilyldiazomethane, which generate alkylidenecarbenes, gives a terminal acetylene from an aldehyde and cyclopentene derivatives from ketones.
Total Synthesis of the Antiviral Natural Product Houttuynoid B
Kerl, Thomas,Berger, Florian,Schmalz, Hans-Günther
supporting information, p. 2935 - 2938 (2016/03/25)
The first total synthesis of houttuynoid B, a powerful antiviral flavonoid glycoside from the Chinese plant Houttuynia cordata, is described. In a key step, a Baker-Venkataraman rearrangement employing an already glycosylated substrate was used to efficiently set up the fully functionalized carbon skeleton. The required benzofuran building block was prepared through a domino Sonogashira coupling/5-endo-dig cyclization and converted into a stable 1-hydroxybenzotriazole-derived active ester prior to linking with a galactosylated hydroxyacetophenone unit. The elaborated synthesis requires only nine steps (11 % overall yield) along the longest linear sequence and paves the way for the preparation of structurally related compounds for further biological evaluation.
A Sequential Homologation of Alkynes and Aldehydes for Chain Elongation with Optional 13C-Labeling
Brunner, Andreas,Hintermann, Lukas
, p. 2787 - 2792 (2016/02/27)
Terminal alkynes (RCCH) are homologated by a sequence of ruthenium-catalyzed anti-Markovnikov hydration of alkyne to aldehyde (RCH2CHO), followed by Bestmann-Ohira alkynylation of aldehyde to chain-elongated alkyne (RCH2CCH). Inverting the sequence by starting from aldehyde brings about the reciprocal homologation of aldehydes instead. The use of 13C-labeled Bestmann-Ohira reagent (dimethyl ((1-13C)-1-diazo-2-oxopropyl)phosphonate) for alkynylation provides straightforward access to singly or, through additional homologation, multiply 13C-labeled alkynes. The labeled alkynes serve as synthetic platform for accessing a multitude of specifically 13C-labeled products. Terminal alkynes with one or two 13C-labels in the alkyne unit have been submitted to alkyne-azide click reactions; the copper-catalyzed version (CuAAC) was found to display a regioselectivity of >50 000:1 for the 1,4- over the 1,5-triazine isomer, as shown analytically by 13C NMR spectroscopy.
Extended structural modulation of bio-inspired chiral lipidic alkynylcarbinols as antitumor pharmacophores
Listunov, Dymytrii,Billot, Chelmia,Joly, Etienne,Fabing, Isabelle,Volovenko, Yulian,Génisson, Yves,Maraval, Valérie,Chauvin, Remi
, p. 7920 - 7930 (2015/09/15)
The chiral alkynylcarbinol motif typically found in natural marine products, has been the subject of intense research activity for its pharmacophoric properties, in particular cytotoxicity against tumor cell lines. In a chemical synthesis-driven four-parameter structure-activity relationship (SAR) study from the (S,E)-eicos-4-en-1-yl-3-ol natural reference 1, the (S)-dialkynylcarbinol unit of the non-natural dehydro derivative 2 emerged as an unprecedented anti-tumoral pharmacophore. An extended study of lipidic alkynylcarbinol pharmacophores is presented, addressing additional structural parameters: Z→E isomerization of the alkenyl carbinol substituent of 1, variation of the lipidic chain length of 2 (C3n, n=3, 4, 6), oxidation or substitution of the carbinol unit of 2 (to ketone, tertiary methylcarbinol, or methylether), cyclomethylenation of the double bond of 1. The synthesis of these analogues is described, including the preparation of enantio-enriched chiral alkynylcarbinol derivatives using a modified Carreira procedure for Zn-mediated addition of (trialkylsilyl)acetylene substrates to ynals in the presence of (-)- or (+)-N-methylephedrine. Preliminary cytotoxicity evaluation of 12 new products against the HCT 116 tumor cell line are finally reported and the results compared with those obtained for 1 and 2. These observations support and refine the relevance of the pharmacophoric character of secondary DAC units.
Synthesis of acetylenes via dehydrobromination using solid anhydrous potassium phosphate as the base under phase-transfer conditions
Shenawi-Khalil, Sanaa,Sonavane, Sachin U.,Sasson, Yoel
experimental part, p. 2295 - 2297 (2012/07/27)
Phase-transfer catalyzed preparation of acetylenes from the corresponding vicinal dibromo compounds via double dehydrobromination using the mild solid base, anhydrous potassium phosphate, under very mild conditions is reported.
Nickel phosphide nanocatalysts for the chemoselective hydrogenation of alkynes
Carenco, Sophie,Leyva-Pérez, Antonio,Concepción, Patricia,Boissire, Cédric,Mézailles, Nicolas,Sanchez, Clément,Corma, Avelino
experimental part, p. 21 - 28 (2012/07/27)
Well-defined 25 nm nickel phosphide nanoparticles act as a colloidal catalyst for the chemoselective hydrogenation of terminal and internal alkynes. Cis-alkenes are obtained in mild conditions with good conversion and selectivity. The phosphorus inserted in the Ni-P nanoparticles is critical for the selectivity of the nanocatalyst. Mechanistic investigations using isotope labeling provide insight on the reactants interaction with the nanoparticles surface. They pinpoint the occurrence of CH bond cleavage in terminal alkynes during the reaction.
Palladium-catalyzed carbon-carbon bond formation and cleavage of organo(hydro)fullerenes
Nambo, Masakazu,Itami, Kenichiro
supporting information; experimental part, p. 4760 - 4764 (2009/12/26)
Palladium-catalyzed reactions of organo-(hydro)fullerenes, new C-C bond formation, and cleaving processes for organo-(hydro)fullerenes were reported. These reactions caused the introduction of various organic fragments and a hydrogen atom to the fullerene
Conversion of bromoalkenes into alkynes by wet tetra-n-butylammonium fluoride
Okutani, Masaru,Mori, Yuji
supporting information; scheme or table, p. 442 - 444 (2009/04/10)
(Chemical Equation Presented) Tetra-n-butylammonium fluoride was found to be a mild and efficient base for the elimination reaction of bromoalkenes. Treatment of 1,1-dibromoalkenes, (Z)-1-bromoalkenes, and internal bromoalkenes with 5 equiv of TBAF·3H2O in DMF yielded terminal and internal alkynes in high yields without undue regard to the presence of water.
Modular approach to the synthesis of unsaturated 1-monoacyl glycerols
Coleman, Bridgett E.,Cwynar, Valerie,Hart, David J.,Havas, Fabien,Jakkam, Madan Mohan,Patterson, Suzanne,Ridenour, Sam,Schmidt, Michael,Smith, Eboney,Wells, Angela J.
, p. 1339 - 1342 (2007/10/03)
A modular synthesis of unsaturated 1-monoacylglycerols (1) from cis-1-iodo-1-alkenes [cis-RCH=CHI] and unsaturated carboxylic acids [CH 2=CH(CH2)nCO2H] is described. The method revolves around a Suzuki coupling to establish olefin geometry.
A convenient scalable one-pot conversion of esters and Weinreb amides to terminal alkynes
Dickson, Hamilton D.,Smith, Stephon C.,Hinkle, Kevin W.
, p. 5597 - 5599 (2007/10/03)
Esters and amides undergo reduction to the corresponding aldehydes using DIBAL-H followed by same pot conversion to terminal alkynes utilizing the Bestmann-Ohira reagent in good to excellent yields. Additionally chiral nonracemic substrates undergo this transformation with complete preservation of stereochemical integrity.
