Synthesis of Aromatic α‐Aminoesters: Palladium‐Catalyzed Long‐Range Arylation of Primary CH Bonds

Abstract

Scheme 4 of this Communication contains two typesetting mistakes that need to be corrected: 1) The text above the chemical formula for 9 a must read "g arylation" instead of "g arylation", and 2) the isomeric ratio for 14 a is "b/g > 98:2" and not "g/b > 98:2".

Selectivity Control in the Palladium-catalyzed Cross-coupling of Alkyl Nucleophiles

“…[8] A different selectivity outcome was observed with enolates 1b derived from α-aminoesters (Scheme 2b). [12] In this case a complete β-selectivity was observed, independent of the nature of the aryl bromide. A second-generation, N-phenylimidazole-based [13] ligand (L 2 ) was found to be superior to L 1 , and afforded good yields for a range of β-arylated products.…”

Palladium-Mediated Organofluorine Chemistry

“…Coupling of fluorinated aryl halides with enolate precursors, 115,116 polyfluorovinyl chlorides with thiophenes, 117 and perfluorophenyl carboxylic acids with arenes have been reported. 118 However, in this section, more attention will be paid to those reactions where C-H activation occurs on the fluorinated coupling partner.…”

Metal‐Catalyzed Sequential Formation of Distant Bonds in Organic Molecules: Palladium‐Catalyzed Hydrosilylation/Cyclization of 1,n‐Dienes by Chain Walking

“…[2] Thec hain-walking mechanism, repetitive b-hydride elimination/reinsertion, allows the migration of the position of the reactive metal-carbon bond on the alkyl chain to create afoothold for the bond formation at the position remote from the original reactive site.T he sequential remote bond formation by chain walking has been achieved for several olefin polymerization reactions using Brookhart-type diimine palladium catalysts. [3] In recent years, rapid progress has been made in the use of the chain-walking mechanism in organic synthesis, [4][5][6][7][8][9][10] but most of the reactions are either initiated by addition of am etal-hydride to an alkene to start the chain walking by installing ah ydrogen atom at the reaction initiation site,o rt erminated by rapid chain-walking isomerization to form at hermodynamically stable product. Therefore,the use of chain walking in organic syntheses for formation of remote bonds between nonhydrogen atoms has been limited to Larocksalkene arylation/chain walking/allylic substitution reactions, [5b-d] which proceed by chain walking to form athermodynamically stable p-allylpalladium intermediate.Achain-walking approach has not been achieved for sequential additions to carbon-carbon multiple bonds,which have been more prevalently explored in metalcatalyzed domino-type reactions.…”