347885-68-1Relevant articles and documents
A mild exchange reaction of xanthates with bromine
Barbier, Francis,Pautrat, Fran?ois,Quiclet-Sire, Béatrice,Zard, Samir Z.
, p. 811 - 813 (2002)
Secondary S-alkyl-O-ethyl (or O-neopentyl) xanthates can be converted into the corresponding bromides by heating with ethyl 2-bromo-2-methylpropionate and cumyl peroxide in refluxing chlorobenzene; this transformation can be coupled to a xanthate transfer radical addition to an olefin.
Merging Halogen-Atom Transfer (XAT) and Cobalt Catalysis to Override E2-Selectivity in the Elimination of Alkyl Halides: A Mild Route towardcontra-Thermodynamic Olefins
Zhao, Huaibo,McMillan, Alastair J.,Constantin, Timothée,Mykura, Rory C.,Juliá, Fabio,Leonori, Daniele
supporting information, p. 14806 - 14813 (2021/09/18)
We report here a mechanistically distinct tactic to carry E2-type eliminations on alkyl halides. This strategy exploits the interplay of α-aminoalkyl radical-mediated halogen-atom transfer (XAT) with desaturative cobalt catalysis. The methodology is high-yielding, tolerates many functionalities, and was used to access industrially relevant materials. In contrast to thermal E2 eliminations where unsymmetrical substrates give regioisomeric mixtures, this approach enables, by fine-tuning of the electronic and steric properties of the cobalt catalyst, to obtain high olefin positional selectivity. This unprecedented mechanistic feature has allowed access tocontra-thermodynamic olefins, elusive by E2 eliminations.
Nickel-Catalyzed Cyanation of Unactivated Alkyl Sulfonates with Zn(CN)2
Xia, Aiyou,Lv, Peizhuo,Xie, Xin,Liu, Yuanhong
supporting information, p. 7842 - 7847 (2020/11/02)
Cyanation of unactivated primary and secondary alkyl mesylates with Zn(CN)2 catalyzed by nickel has been developed. The reaction provides an efficient route for the synthesis of alkyl nitriles with wide substrate scope, good functional group tolerance, and compatibility with heterocyclic compounds. Mechanistic studies indicate that alkyl iodide generated in situ serves as the reactive intermediate and the gradual release of alkyl iodide is crucial for the success of the reaction.
