75266-40-9Relevant academic research and scientific papers
Radical-Mediated Acyl Thiol-Ene Reaction for Rapid Synthesis of Biomolecular Thioester Derivatives
Lynch, Dylan M.,McLean, Joshua T.,McSweeney, Lauren,Milbeo, Pierre,Scanlan, Eoin M.
, p. 4148 - 4160 (2021/08/24)
The thiol-ene ‘click’ reaction has emerged as a versatile process for carbon–sulfur bond formation with widespread applications in chemical biology, medicinal chemistry and materials science. Thioesters are key intermediates in a wide range of synthetic and biological processes and efficient methods for their synthesis are of considerable interest. Herein, we report the first examples of acyl-thiol-ene (ATE) for the synthesis of biomolecular thioesters, including peptide, lipid and carbohydrate derivatives. A key finding is the profound effect of the amino acid side chain on the outcome of the ATE reaction. Furthermore, radical generated thioesters underwent efficient S-to-N acyl transfer and desulfurisation to furnish ‘sulfur-free’ ligation products in an overall amidation process with diverse applications for chemical ligation and bioconjugation.
Chemoselective Arylation of Dialkyl Diselenides and Application to the Synthesis of a ε-N,N,N-Trimethyllysine Derivative
Takahashi, Ryuhei,Sakamoto, Kenta,Umezawa, Naoki,Umehara, Takashi,Matsuo, Jun-ichi
supporting information, p. 6649 - 6652 (2020/10/19)
Nucleophilic aromatic substitution of a dialkyl diselenide with 1-bromo-2,4-dinitrobenzene and sodium borohydride in EtOH/THF proceeded chemoselectively in the presence of a thiol, an amine, and a carboxylic acid. ε-N,N,N-Trimethyllysine derivative was synthesized from selenohomocysteine dimer by the present arylation, oxidation, cross-metathesis with 4-iodobutene, reduction, and substitution with trimethylamine.
Macrocyclic cysteine protease inhibitors and compositions thereof
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, (2016/09/26)
The present invention provides a novel class of macrocyclic compounds, which are useful as cysteine protease inhibitors. Also provided are novel intermediates and methods of preparing the compounds. The invention also provides pharmaceutical compositions
Continuous-flow thermolysis for the preparation of vinylglycine derivatives
Lamborelle, Nicolas,Simon, Justine F.,Luxen, André,Monbaliu, Jean-Christophe M.
, p. 11602 - 11606 (2015/12/08)
Syn sulfoxide elimination was carried out under continuous-flow conditions in a mesofluidic thermolysis reactor. The design of the reactor enabled accurate control of reaction time and conditions, affording a convenient scale-independent procedure for the production of N,C-protected vinylglycine derivatives. Thermolysis at 270 °C under 1000 psi of pressure in superheated toluene enabled typical daily outputs ranging from 11 to 46 g per day with excellent selectivities and ee (>97%). The various competitive reaction pathways were studied and rationalized according to a computational study.
A convergent synthesis of carbocyclic sinefungin and its C-5 epimer
Ghosh, Arun K.,Lv, Kai
, p. 6761 - 6768 (2016/02/18)
A convergent synthesis of carbocyclic sinefungin (2), its C-5 epimer 3a, and adenine-modified derivative 3b is described. The key features of our approach include the use of commercially available L-methionine and readily available (1R,4S)-4-hydroxy-2-cyclopentenyl acetate as starting materials, a cross-metathesis reaction, an enzymatic kinetic resolution, and a Staudinger reduction. The current synthesis is flexible and, therefore, provides convenient access to the synthesis of various carbocyclic sinefungin analogues for biological evaluation. A convergent synthesis of carbocyclic sinefungin (2), its C-5 epimer 3a, and adenine-modified derivative 3b is described. The key features of this approach include the use of commercially available L-methionine and readily available (1R,4S)-4-hydroxy-2-cyclopentenyl acetate, a cross-metathesis reaction, an enzymatic kinetic resolution, and a Staudinger reduction.
Macrocyclic Cysteine Protease Inhibitors and Compositions Thereof
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, (2011/02/18)
The present invention provides a novel class of macrocyclic compounds, which are useful as cysteine protease inhibitors. Also provided are novel intermediates and methods of preparing the compounds. The invention also provides pharmaceutical compositions
PREPARATION OF ALKENES BY MILD THERMOLYSIS OF SULFOXIDES
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Page/Page column 31-32, (2010/07/02)
Embodiments of this disclosure, among others, encompass methods for generating alkenes under mild thermolytic conditions that can provide almost total conversion of a precursor compound to an alkene without isomerization or the need to chromatographically purify the final product By selectively blocking the amino and carboxy groups of the depvatized amino acid, the methods of the disclosure provide for the synthesis of a peptide having the vinylglycine moiety at either the carboxy or the amino terminus of the peptide The mild conditions for the thermolytic removal of an o-NO2-phenyl substituted aryl group ensure that there is minimal if any damage to thermally sensitive conjugates such as a peptide bearing the vinylglycine The methods of the present disclosure have practical applications for the preparation of unsaturated compounds under mild, thermolytic conditions.
An improved protocol for the preparation of (S)-vinylglycine from (S)-methionine
Kuechenthal,Migenda, Julia,Polednia, Magdalena,Maison, Wolfgang
scheme or table, p. 443 - 448 (2010/11/17)
We present an optimized procedure for the synthesis of (S)-vinylglycine from (S)-methionine. The key step is a solvent free pyrolysis of an intermediate sulfoxide at high temperature. Using our optimized reaction conditions, Cbz-protected vinylglycine was
Preparation of vinylglycines by thermolysis of homocysteine sulfoxides
Patel, Sravan Kumar,Long, Timothy E.
supporting information; experimental part, p. 5067 - 5070 (2009/12/01)
The synthesis and efficacy of preparing Cbz-VG-OMe (1) by thermolysis of alkyl and aryl homocysteine sulfoxides were surveyed. This investigation determined that aryl sulfoxide analogs were more effective for the reaction and that the 2-nitrophenyl analog 10f possessed a unique ability to syn eliminate at temperatures as low as 100 °C. The thermolysis of sulfoxide 10f was additionally discovered to occur under toluene reflux and when sodium acetate was added, Cbz-VG-OMe (1) could be obtained in high purity by simple filtration of the precipitated sulfenic acid byproduct 12. This mild protocol which was also applied in the synthesis of VG dipeptide 13 would have utility in the general synthesis of olefins and alkenes from 2-nitrophenylsulfoxides.
Enantiospecific synthesis of (+)-hyacinthacine A2
Dewi-Wülfing, Purnama,Blechert, Siegfried
, p. 1852 - 1856 (2007/10/03)
We report an efficient synthesis of (+)-hyacinthacine A2 in six steps from (S)-N-Cbz-vinylgylcine. The key strategies were the olefin cross metathesis (CM), Sharpless asymmetric dihydroxylation, and a sequential double reductive cyclization. Wi
