26155-19-1Relevant articles and documents
Pd(II)-Catalyzed CC Bond Cleavage by a Formal Group-Exchange Reaction
Ye, Runyou,Zhu, Maoshuai,Yan, Xufei,Long, Yang,Xia, Ying,Zhou, Xiangge
, p. 8678 - 8683 (2021/07/26)
A chelation-assisted palladium-catalyzed CC bond cleavage of α, β-unsaturated ketone to form alkenyl nitrile in the presence of nitrile is disclosed on the basis of a formal group-exchange reaction formulated as C1C2 + C3 → C1C3 + C2, differing from normal alkene oxidative cleavage and metathesis type. The isolated key active Pd(II) complex as well as deuterium-labeled experiment revealed the necessity of the chelation group, and a plausible catalytic pathway was proposed.
Synthesis of Tetrahydroisoquinolines by Visible-Light-Mediated 6- exo -trig Cyclization of α-Aminoalkyl Radicals
Bach, Thorsten,Grübel, Michael,Jandl, Christian
supporting information, p. 1825 - 1829 (2019/09/09)
Starting from the respective tertiary α-silylmethyl amines, the intramolecular cyclization of α-aminoalkyl radicals to Michael acceptors produced tetrahydroisoquinolines. The reaction conditions included the use of 5 molpercent of an iridium photoredox catalyst, dimethylformamide as the solvent, and equimolar amounts of water and cesium carbonate as the additives. 13 substrates were synthesized from ortho -alkylbenzaldehydes in a three-step procedure involving a carbonyl condensation, a radical bromination, and a substitution by a secondary α-silylmethyl amine. After optimization of the photocyclization, the reaction delivered tetrahydroisoquinolines in moderate to high yields (41-83percent). A facial diastereoselectivity (dr ? 80:20) was observed with chiral substrates and a crystal structure provided evidence for the relative configuration of the major diastereoisomer. A catalytic cycle with direct electron transfer to the photoexcited metal catalyst is proposed.
meta-Selective C?H Borylation of Benzylamine-, Phenethylamine-, and Phenylpropylamine-Derived Amides Enabled by a Single Anionic Ligand
Davis, Holly J.,Genov, Georgi R.,Phipps, Robert J.
supporting information, p. 13351 - 13355 (2017/10/07)
Selective functionalization at the meta position of arenes remains a significant challenge. In this work, we demonstrate that a single anionic bipyridine ligand bearing a remote sulfonate group enables selective iridium-catalyzed borylation of a range of common amine-containing aromatic molecules at the arene meta position. We propose that this selectivity is the result of a key hydrogen bonding interaction between the substrate and catalyst. The scope of this meta-selective borylation is demonstrated on amides derived from benzylamines, phenethylamines and phenylpropylamines; amine-containing building blocks of great utility in many applications.
