Radical 1,4-Aryl Migration Enabled Remote Cross-Electrophile Coupling of 浼?Amino-灏?Bromo Acid Esters with Aryl Bromides was written by Tang, Shi;Xu, Zhen-Hua;Liu, Ting;Wang, Shuo-Wen;Yu, Jian;Liu, Jian;Hong, Yu;Chen, Shi-Lu;He, Jin;Li, Jin-Heng. And the article was included in Angewandte Chemie, International Edition in 2021.Synthetic Route of C8H7BrO2 This article mentions the following:
Here an unprecedented, efficient nickel-catalyzed radical relay was reported for the remote cross-electrophile coupling of 灏?bromo-浼?benzylamino acid esters with aryl bromides via 1,4-aryl migration/arylation cascades. 灏?Bromo-浼?benzylamino acid esters were considered as unique mol. scaffolds allowing for aryl migration reactions, which were conceptually novel variants for the radical Truce-Smiles rearrangement. This reaction enabled the formation of two new C(sp3)-C(sp2) bonds using a bench-stable Ni/bipyridine/Zn system featuring a broad substrate scope and excellent diastereoselectivity, which provided an effective platform for the remote aryl group migration and arylation of amino acid esters via redox-neutral C(sp3)-C(sp2) bond cleavage. Mechanistically, this cascade reaction was accomplished by combining two powerful catalytic cycles consisting of a cross-electrophile coupling and radical 1,4-aryl migration through the generation of C(sp3)-centered radical intermediates from the homolysis of C(sp3)-Br bonds and the switching of the transient alkyl radical into a robust 浼?aminoalkyl radical. In the experiment, the researchers used many compounds, for example, 3-Bromophenyl acetate (cas: 35065-86-2Synthetic Route of C8H7BrO2).
3-Bromophenyl acetate (cas: 35065-86-2) belongs to organobromine compounds. Bromine is more electronegative than carbon (2.9 vs 2.5). Consequently, the carbon in a carbon閳ユ彽romine bond is electrophilic, i.e. alkyl bromides are alkylating agents. In the pharmaceutical industry organo bromine derivatives are used as sedatives, vasodilators, antiseptic agents, and anticancer agents.Synthetic Route of C8H7BrO2
Referemce:
Bromide – Wikipedia,
bromide – Wiktionary