- Radical-Mediated Acyl Thiol-Ene Reaction for Rapid Synthesis of Biomolecular Thioester Derivatives
-
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.
- Lynch, Dylan M.,McLean, Joshua T.,McSweeney, Lauren,Milbeo, Pierre,Scanlan, Eoin M.
-
supporting information
p. 4148 - 4160
(2021/08/24)
-
- Atmospheric Oxygen Mediated Radical Hydrothiolation of Alkenes
-
A mild, metal-free, atmospheric oxygen-mediated radical hydrothiolation of alkenes (and alkyne) is reported. A variety of sulfur containing motifs including alkanethiols, thiophenols and thioacids undergo an atmospheric oxygen-mediated radical hydrothiolation reaction with a plethora of alkenes in good yield with excellent functional group compatibility, typically with short reaction times to furnish a range of functionalized products. Biomolecules proved tolerant to the conditions and the procedure is robust and easily executable requiring no specialized equipment. Concise mechanistic studies confirm the process proceeds through radical intermediates in a thiol-ene reaction manifold. The methodology offers an efficient “green” approach for thiol-ene mediated “click” ligation and a milder alternative to thermally initiated hydrothiolation processes.
- McCourt, Ruairí O.,Scanlan, Eoin M.
-
supporting information
p. 15804 - 15810
(2020/10/26)
-
- An easy and efficient method for the production of carboxylic acids and aldehydes by microbial oxidation of primary alcohols
-
An easy and efficient methodology for obtaining aldehydes or carboxylic acids by oxidation of the corresponding primary alcohols with acetic acid bacteria is reported. When the biotransformation is performed in water the acids are obtained; aldehydes can be accumulated by using a water/isooctane two-liquid phase system.
- Gandolfi, Raffaella,Ferrara, Nicola,Molinari, Francesco
-
p. 513 - 514
(2007/10/03)
-
- Microwave assisted Willgerodt-Kindler reaction of styrenes
-
Styrenes are efficiently transformed to thioamides via the Willgerodt- Kindler reaction under microwave irradiation.
- Moghaddam, Firouz Matloubi,Ghaffarzadeh, Mohammad,Dakamin, Mohammad G.
-
p. 228 - 229
(2007/10/03)
-
- Method of preparing a thiophene-containing or furan-containing conjugated compound and precursor compound used therein
-
The invention relates to a method of preparing thiophene-containing or furan-containing conjugated compounds such as polythiophene. The method uses a precursor compound having tetrahydrothiophene or tetrahydrofuran precursor units having arylthio or alkylthio substituents. The precursor units can be thermally converted into thiophene or furan units. Due to the presence of the precursor units the precursor compound is soluble and can, unlike the corresponding conjugated compound, be processed from solution.
- -
-
-
- Pesticidal compositions containing phosphoric esters and divalent sulphur compounds
-
Pesticidal composition comprising: a pesticidal, phosphoric ester the molecule of which has at least one alkyl group of 1 to 3 carbon atoms, 0.05 to 10% of an agent stabilizing the said ester against decomposition by protonisation, together with adjuvants characterized in that the stabilizing agent comprises at least one sulphur compound containing per molecule at least one divalent sulphur atom of which one valence is bonded to an atom chosen from sulphur, carbon, nitrogen, hydrogen, and metals capable of giving a salt, the other valence being bonded to an atom chosen from hydrogen, the carbon atom already noted, a second carbon atom, the nitrogen atom already noted, a second nitrogen atom, the metal atom already noted in the case of a metal of valence greater than one, a second atom of metal and oxygen when the first valence is not attached to an atom of hydrogen, the proportion of sulphur calculated with reference to the weight of the sulphur compound being between 5 and 99%. Process for stabilizing a phosphoric ester of which the molecule possesses at least one alkyl group containing 1 to 3 carbon atoms characterized in that there is added to the phosphoric ester or to a mixture which contains it, 0.05 to 10% calculated on the weight of the phosphoric acid ester of an agent capable of stabilizing the said phosphoric ester against protonisation and comprising at least one sulphur compound such as that defined thereupon.
- -
-
-