4341-76-8Relevant articles and documents
C-Alkylation of αβ-Acetylenic Esters using Electrochemically Generated Intermediates
Tokuda, Masao,Nishio, Osamu
, p. 188 - 189 (1980)
Electrolysis at a platinum cathode of ethyl alk-2-ynoates in the presence of an excess of alkyl iodide in hexamethylphosphoramide or dimethylformamide solution containing tetra-n-butylammonium iodide gave the corresponding non-conjugated dialkylation products, ethyl 2,2-dialkylalk-3-ynoates, in good yield.
One-pot mild and efficient synthesis of [1,3]thiazino[3,2-: A] indol-4-ones and their anti-proliferative activity
Rhodes, Steven,Short, Spencer,Sharma, Sidhika,Kaur, Ramneet,Jha, Mukund
supporting information, p. 3914 - 3920 (2019/04/30)
A base mediated environmentally benign one-pot efficient methodology has been developed for the synthesis of [1,3]thiazino[3,2-a]indol-4-ones using indoline-2-thiones and propiolate esters in aqueous medium. The conjugate addition of thiones first results in ethyl (3-(indol-2-yl)thio)acrylates in situ, which subsequently undergoes intramolecular cyclization to produce indole-fused thiazin-4-ones in good to excellent yields. The cytotoxic screening of the synthesized compounds using MTT assay revealed the anti-proliferative nature of these frameworks against triple negative breast cancer cell lines with the highest activity emanating from 4H-[1,3]thiazino[3,2-a]indol-4-one and 8-methyl-2-propyl-4H-[1,3]thiazino[3,2-a]indol-4-one compounds.
Convergent One-Pot Oxidative [n + 1] Approaches to Spiroacetal Synthesis
Peh, Guangrong,Floreancig, Paul E.
supporting information, p. 3750 - 3753 (2015/08/18)
Two one-pot oxidative annulative approaches to spiroacetal synthesis are described. One approach uses a Lewis acid mediated Ferrier reaction in the fragment-coupling stage followed by DDQ-promoted oxidative carbon-hydrogen bond cleavage and cyclization. An alternative approach employs a Heck reaction for fragment coupling followed by DDQ-mediated enone formation and cyclization. These strategies provide convergent routes to common subunits in natural products, medicinal agents, and chemical libraries under mild reaction conditions.
SPIRO-LACTAM NMDA RECEPTOR MODULATORS AND USES THEREOF
-
Paragraph 00303; page 125, (2014/08/19)
Disclosed are compounds having enhanced potency in the modulation of NMDA receptor activity. Such compounds are contemplated for use in the treatment of conditions such as depression and related disorders. Orally available formulations and other pharmaceutically acceptable delivery forms of the compounds, including intravenous formulations, are also disclosed.
Copper(II)-catalyzed silylation of activated alkynes in water: Diastereodivergent access to E- or Z-β-silyl-α,β-unsaturated carbonyl and carboxyl compounds
Calderone, Joseph A.,Santos, Webster L.
supporting information, p. 4154 - 4158 (2014/05/06)
Copper(II)-catalyzed silylation of substituted alkynylcarbonyl compounds was investigated. Through the activation of Me2PhSiBpin in water at room temperature and open atmosphere, vinylsilanes conjugated to carbonyl groups are synthesized in high yield. A surprising diastereodivergent access to olefin geometry was discovered using a silyl conjugate addition strategy: aldehydes and ketones were Z selective while esters and amides were exclusively transformed into the E products. Dial a diastereomer: The title reaction proceeds through the activation of Me2PhSiBpin in water at room temperature and open atmosphere to produce high yields of vinylsilanes conjugated to carbonyl groups. A surprising diastereodivergent access to olefin geometry was discovered using this silyl conjugate addition strategy: aldehydes were Z selective while esters and amides exclusively delivered the E-configured products.
Selective one-pot synthesis of allenyl and alkynyl esters from β-ketoesters
Maity, Pradip,Lepore, Salvatore D.
supporting information; experimental part, p. 158 - 162 (2009/04/07)
(Chemical Equation Presented) A convenient method is described for the dehydration of β-ketoesters to generate conjugated and deconjugated alkynyl esters and conjugated allenyl esters. This sequential one-pot method involves the formation of a vinyl trifl
The asymmetric aza-claisen rearrangement: development of widely applicable pentaphenylferrocenyl palladacycle catalysts
Fischer, Daniel F.,Barakat, Assem,Xin, Zhuo-Qun,Weiss, Matthias E.,Peters, Rene
supporting information; experimental part, p. 8722 - 8741 (2010/03/31)
Systematic studies have been performed to develop highly efficient catalysts for the asymmetric aza-Claisen rearrangement of trihaloacetimidates. Herein, we describe the stepwise development of these catalyst systems involving four different catalyst generations finally resulting in the development of a planar chiral pentaphenylferrocenyl oxazoline palladacycle. This complex is more reactive and has a broader substrate tolerance than all previously known catalyst systems for asymmetric aza-Claisen rearrange-ments. Our investigations also reveal that subtle changes can have a big impact on the activity. With the enhanced catalyst activity, the asymmetric aza-Claisen rearrangement has a very broad scope: the methodology not only allows the formation of highly enantioenriched primary allylic amines, but also secondary and tertiary amines; al-lylic amines with N-substituted quaternary stereocenters are conveniently accessible as well. The reaction conditions tolerate many important functional groups, thus providing stereoselective access to valuable functionalized building blocks, for example, for the synthesis of unnatural amino acids. Our results suggest that face-selective olefin coordination is the enantioselectivitydetermining step, which is almost exclusively controlled by the element of planar chirality.
Asymmetric formation of allylic amines with N-substituted quaternary stereocenters by PdII-catalyzed aza-Claisen rearrangements
Fischer, Daniel F.,Xin, Zhuo-Qun,Peters, Rene
, p. 7704 - 7707 (2008/09/18)
(Chemical Equation Presented) With the ferrocene imidazoline palladacycle FIP-Cl as precatalyst, quaternary N-substituted stereocenters can be generated in an asymmetric aza-Claisen rearrangement. Excellent enantioselectivities are obtained even if R and R′ have a similar or identical size (see scheme: e.g. 96% ee for CH3/CD3).
Palladium-catalyzed synthesis of N-vinyl pyrroles and indoles
Movassaghi, Mohammad,Ondrus, Alison E.
, p. 8638 - 8641 (2007/10/03)
A stereospecific palladium-catalyzed N-vinylation of aza-heterocycles with vinyl inflates is described. Cyclic and acyclic vinyl triflates along with nonnucleophilic azaheterocycles were found to be substrates for this palladium-catalyzed synthesis of N-vinyl pyrrole and indole derivatives.
Total synthesis of (+)-amphidinolide A. Assembly of the fragments
Trost, Barry M.,Wrobleski, Stephen T.,Chisholm, John D.,Harrington, Paul E.,Jung, Michael
, p. 13589 - 13597 (2007/10/03)
The structure elucidation of (+)-amphidinolide A, a cytotoxic macrolide, has been accomplished by employing a combination of total synthesis and NMR spectroscopic analysis. Amphidinolide A possesses two skipped 1,4-diene subunits which are accessible by ruthenium-catalyzed alkene-alkyne couplings. Previous total syntheses had revealed that the reported structure was incorrect; therefore, to incorporate maximum flexibility into the synthesis, with the ultimate goal of determining the correct structure, a highly convergent approach was chosen. Furthermore, liberal use was made of catalytic asymmetric transformations to set individual stereocenters. Three different strategies were envisioned for the end game, and due to the highly convergent nature of the synthesis, all three routes disconnect to the same three key intermediates, 5, 6, and 7. Diastereomers of 6 and 7 were easily prepared by modification of the synthetic routes to allow access to multiple diastereomers of 1 for structural determination.
