A novel catalyst 2 for Wittig-type and dehalogenation reactions was developed. In the presence of triphenyl phosphite, a wide variety of aldehydes could react with alpha-bromoacetates to afford alpha,beta-unsaturated esters or ketones in high yields with excellent E-stereoselectivity when 1-2 mol % of compound 2 was used. Compound 2 was also an effective catalyst for reductive dehalogenation of alpha-bromocarbonyl compounds. The mechanisms for the above reactions were also proposed.
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ACS Omega
April 2022
Division of Molecular Science, Graduate School of Science and Technology, Gunma University, Tenjincho, Kiryu, Gunma 376-8515, Japan.
A series of oligo(thiophene)-modified "soluble" star-shaped ring-opening metathesis polymerization (ROMP) polymers were prepared by sequential living ROMP of norbornene and a cross-linking agent using a molybdenum-alkylidene catalyst, followed by Wittig-type coupling for termination with oligo(thiophene) carboxaldehydes. The resultant star-shaped ROMP polymers displayed unique emission properties affected by the core size and arm repeat units as well as the kind of oligothiophene coated. The effects of the thiophene groups on photophysical properties of star-shaped/linear polymers were studied time-resolved fluorescence spectroscopy.
View Article and Find Full Text PDFJ Org Chem
September 2021
Catalysis Research Laboratory (CaRLa), Im Neuenheimer Feld 584, D-69120 Heidelberg, Germany.
The vinylation of various nucleophiles with acetylene at a maximum pressure of 1.5 bar is achieved by organocatalysis with easily accessible phosphines like tri--butylphosphine. A detailed mechanistic investigation by quantum-chemical and experimental methods supports a nucleophilic activation of acetylene by the phosphine catalyst.
View Article and Find Full Text PDFMolecules
February 2021
Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Hungary.
The purpose of this review is to summarize the importance of microwave (MW) irradiation as a kind of catalyst in organophosphorus chemistry. Slow or reluctant reactions, such as the Diels-Alder cycloaddition or an inverse-Wittig type reaction, may be performed efficiently under MW irradiation. The direct esterification of phosphinic and phosphonic acids, which is practically impossible on conventional heating, may be realized under MW conditions.
View Article and Find Full Text PDFOrg Lett
October 2017
Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.
Electrophilic difluoromethylidenation of dithioesters was achieved in high yields via the reaction with difluorocarbene. When aryl or alkyl dithiocarboxylates were treated with trimethylsilyl 2,2-difluoro-2-fluorosulfonylacetate in the presence of 5 mol % of a Proton Sponge catalyst, the in situ generated difluorocarbene reacted with the dithioesters to afford 2-sulfanylated 1,1-difluoro-1-alkenes via difluorothiiranes. This reaction can be considered as an electrophilic counterpart of the Wittig-type difluoromethylidenation of carbonyl compounds with nucleophilic difluoromethylene ylides.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
May 2017
Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami Osawa, Hachioji, Tokyo, 192-0376, Japan.
A series of end-functionalized poly(9,9'-di-n-octylfluorene vinylene)s (EF-PFVs) with different end groups were obtained by 1) synthesizing EF-PFV with vinyl end groups by acyclic diene metathesis (ADMET) polymerization with a molybdenum catalyst and termination with an aldehyde and 2) subsequent olefin metathesis of the vinyl group with the molybdenum catalyst followed by Wittig-type coupling with another aldehyde. The exclusive formation of EF-PFVs containing a vinyl end group by the ADMET polymerization was confirmed by grafting PEG, and by the synthesis of amphiphilic triblock copolymers by combining atom transfer radical polymerization from the PFV chain end with PEG grafting through a click reaction. Various EF-PFVs with different end groups, such as C F , pyridyl, ferrocenyl, and terthiophene, have thus been prepared.
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