Reactions of nitroxides 15. Cinnamates bearing a nitroxyl moiety synthesized using a Mizoroki–Heck cross-coupling reaction

• Jerzy Zakrzewski and
• Bogumiła Huras

Beilstein J. Org. Chem. 2015, 11, 1155–1162, doi:10.3762/bjoc.11.130

• Mizoroki–Heck cross-coupling reaction between 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl and iodobenzene derivatives in the presence of palladium(II) acetate coordinated with a tri(o-tolyl)phosphine ligand immobilized in a polyurea matrix. Keywords: 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1

• interesting, because it allows for the study of cinnamates using spin labeling methods. To accomplish the synthesis of cinnamates bearing a nitroxyl moiety, we applied a Mizoroki–Heck cross-coupling reaction, using 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (3, an olefin component bearing a nitroxyl

• compounds. Results and Disscusion 4-Acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (3) was obtained in 90–95% yield by the reaction of acryloyl chloride (2) with 2,2,6,6-tetramethyl-4-piperidinol-1-oxyl (1) in the presence of triethylamine [21][34][35][36]. The couplings of 4-acryloyloxy-2,2,6,6

Reactions of nitroxides XIII: Synthesis of the Morita–Baylis–Hillman adducts bearing a nitroxyl moiety using 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a starting compound, and DABCO and quinuclidine as catalysts

• Jerzy Zakrzewski

Beilstein J. Org. Chem. 2012, 8, 1515–1522, doi:10.3762/bjoc.8.171

• Jerzy Zakrzewski Institute of Industrial Organic Chemistry, Annopol 6, 03-236 Warsaw, Poland 10.3762/bjoc.8.171 Abstract The Morita–Baylis–Hillman adducts bearing a nitroxyl moiety were synthesized from 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl and aliphatic, aryl and heterocyclic

• aldehydes. Keywords: 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl; DABCO; Morita–Baylis–Hillman reaction; nitroxides; quinuclidine; Introduction In the Morita–Baylis–Hillman (MBH) reaction, aldehydes react with a double bond activated by an electron-withdrawing group (EWG). The vinylic carbon

• nitroxide moiety on the MBH reaction is unknown. Herein we present the MBH reaction with a nitroxyl radical, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, used as a starting material as an olefin activated with EWG. Acrylates are considered as rather unreactive in the MBH reaction [44]. It was shown