1595-08-0Relevant academic research and scientific papers
Rhodium-Catalyzed Alkenylation of Toluene Using 1-Pentene: Regioselectivity to Generate Precursors for Bicyclic Compounds
Liebov, Nichole S.,Zhu, Weihao,Chen, Junqi,Webster-Gardiner, Michael S.,Schinski, William L.,Gunnoe, T. Brent
, p. 3844 - 3851 (2019)
Rhodium catalysts for arene alkenylation reported by our group (e.g., Science 2015, 348, 421; J. Am. Chem. Soc. 2017, 139, 5474; J. Am. Chem. Soc. 2018, 140, 17007) have demonstrated selectivity for 1-aryl alkenes over y-aryl alkenes (y > 1). This selectivity is notable because 1-aryl alkenes or 1-aryl alkanes cannot be generated using acid-based Friedel-Crafts arene alkylation or acidic zeolite catalysts. Herein, we report the extension of Rh arene alkenylation catalysis to generate 1-tolyl-1-pentenes, which are potential precursors for bicyclic compounds. The olefin concentration, copper(II) oxidant identity and concentration, reaction temperature, and rhodium concentration for the alkenylation of toluene with 1-pentene have been optimized using [Rh(Η2-C2H4)2(μ-OAc)]2 as the catalyst precursor. The rhodium-based catalysis achieves up to 12(1):1 anti-Markovnikov selectivity for 1-tolyl-1-pentenes over 2-tolyl-2-pentenes and is selective for alkenylation in the meta and para positions.
Reactivity of mixed organozinc and mixed organocopper reagents: 6. Nickel-catalyzed coupling of methylarylzincs with primary alkyl halides; An atom-economic aryl-alkyl coupling
Pekel, ?zgen ?mür,Erdik, Ender
experimental part, p. 7087 - 7090 (2012/01/06)
A nickel-catalyzed process for the cross-coupling of mixed arylzincs and primary alkyl halides has been developed. The reaction of a methylarylzinc with a primary alkyl halide in THF in the presence of NiCl2/PPh 3 takes place with selective aryl transfer at room temperature in moderate yields. This protocol provides an atom-economic alternative to aryl-primary alkyl coupling using diarylzincs.
