2114-39-8Relevant articles and documents
Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes
Cruz, Daniel A.,Sinka, Victoria,De Armas, Pedro,Steingruber, Hugo Sebastian,Fernández, Israel,Martín, Víctor S.,Miranda, Pedro O.,Padrón, Juan I.
supporting information, p. 6105 - 6109 (2021/08/18)
A new method that allows the complete control of the regioselectivity of the hydrobromination reaction of alkenes is described. Herein, we report a radical procedure with TMSBr and oxygen as common reagents, where the formation of the anti-Markovnikov product occurs in the presence of parts per million amounts of the Cu(I) species and the formation of the Markovnikov product occurs in the presence of 30 mol % iron(II) bromide. Density functional theory calculations combined with Fukui's radical susceptibilities support the obtained results.
Enantiospecific Solvolytic Functionalization of Bromochlorides
Burckle, Alexander J.,Gál, Bálint,Seidl, Frederick J.,Vasilev, Vasil H.,Burns, Noah Z.
supporting information, p. 13562 - 13569 (2017/10/05)
Herein, we report that under mild solvolytic conditions, enantioenriched bromochlorides can be ionized, stereospecifically cyclized to an array of complex bromocyclic scaffolds, or intermolecularly trapped by exogenous nucleophiles. Mechanistic investigations support an ionic mechanism wherein the bromochloride serves as an enantioenriched bromonium surrogate. Several natural product-relevant motifs are accessed in enantioenriched form for the first time with high levels of stereocontrol, and this technology is applied to the scalable synthesis of a polycyclic brominated natural product. Arrays of nucleophiles including olefins, alkynes, heterocycles, and epoxides are competent traps in the bromonium-induced cyclizations, leading to the formation of enantioenriched mono-, bi-, and tricyclic products. This strategy is further amenable to intermolecular coupling between cinnamyl bromochlorides and a diverse set of commercially available nucleophiles. Collectively, this work demonstrates that enantioenriched bromonium chlorides are configurationally stable under solvolytic conditions in the presence of a variety of functional groups.
Alkylboronic esters from palladium- and nickel-catalyzed borylation of primary and secondary alkyl bromides
Yi, Jun,Liu, Jin-Hui,Liang, Jun,Dai, Jian-Jun,Yang, Chu-Ting,Fu, Yao,Liu, Lei
supporting information; experimental part, p. 1685 - 1691 (2012/07/28)
Palladium- and nickel-catalyzed cross-coupling recations of unactivated alkyl bromides with diboron reagents have been developed as practical methods for the synthesis of primary and secondary alkylboronic esters. These reactions extend the concept and utility of Pd- and Ni-catalyzed cross-coupling of aliphatic electrophiles. They also show different substrate selectivity and ligand dependence as compared to the recently reported Cu-catalyzed borylation reaction. Copyright