72410-96-9Relevant academic research and scientific papers
Photocatalytic Atom-Transfer Radical Addition of Activated Chlorides to Alkenes
Kostromitin, Vladislav S.,Zemtsov, Artem A.,Levin, Vitalij V.,Dilman, Alexander D.
, p. 5336 - 5340 (2021/11/03)
A protocol for performing atom transfer radical addition of activated alkyl chlorides to alkenes is described. The reaction is promoted by blue light in the presence of an organic photocatalyst (3DPA2FBN), serving to generate free radicals, and a copper c
Visible-light-induced addition of carboxymethanide to styrene from monochloroacetic acid
Brouwer, Albert M.,De Bruin, Bas,Van Leeuwen, Nicole S.,Van Vliet, Kaj M.
supporting information, p. 398 - 408 (2020/03/27)
Where monochloroacetic acid is widely used as a starting material for the synthesis of relevant groups of compounds, many of these synthetic procedures are based on nucleophilic substitution of the carbon chlorine bond. Oxidative or reductive activation of monochloroacetic acid results in radical intermediates, leading to reactivity different from the traditional reactivity of this compound. Here, we investigated the possibility of applying monochloroacetic acid as a substrate for photoredox catalysis with styrene to directly produce γ-phenyl-γ-butyrolactone. Instead of using nucleophilic substitution, we cleaved the carbon chlorine bond by single-electron reduction, creating a radical species. We observed that the reaction works best in nonpolar solvents. The reaction does not go to full conversion, but selectively forms γ-phenyl-γ-butyrolactone and 4-chloro-4-phenylbutanoic acid. Over time the catalyst precipitates from solution (perhaps in a decomposed form in case of fac-[Ir(ppy)3]), which was proven by mass spectrometry and EPR spectroscopy for one of the catalysts (N,N-5,10-di(2-naphthalene)-5,10-dihydrophenazine) used in this work. The generation of HCl resulting from lactone formation could be an additional problem for organometallic photoredox catalysts used in this reaction. In an attempt to trap one of the radical intermediates with TEMPO, we observed a compound indicating the generation of a chloromethyl radical.
A New Method for Generating Trichlorotitanium(IV) Ester Homoenolates. Direct Tin-Titanium Exchange
Goswami, Ramanuj
, p. 5907 - 5909 (2007/10/02)
Treatment of the β-tri-n-butylstannyl derivatives of esters with titanium tetrachloride in dichloromethane effects tin-titanium exchange to generate trichlorotitanium(IV) homoenolate derivatives of the esters, which may then be used in further reaction with electrophiles.
