160805-54-9Relevant articles and documents
Remote sp3 C–H Amination of Alkenes with Nitroarenes
Xiao, Jichao,He, Yuli,Ye, Feng,Zhu, Shaolin
, p. 1645 - 1657 (2018/05/16)
Direct installation of a functional group at remote, unfunctionalized sites in an alkyl chain is a synthetically valuable but rarely reported process. The remote relay hydroarylamination of distal and proximal olefins, and of olefin isomeric mixtures, has been achieved through NiH-catalyzed alkene isomerization and sequential reductive hydroarylamination with nitroarenes. This provides an attractive approach to the direct installation of a distal arylamino group within alkyl chains. The single-step conversion of simple olefins and nitro(hetero)arenes to value-added arylamines is a practical strategy for amine synthesis as well as the remote activation of sp3 C–H bonds. The value of this transformation is further supported by the regioconvergent arylamination of isomeric mixtures of olefins. Modern organic synthesis requires more efficient strategies, such as C–H functionalization, with which to construct complex molecules from readily available chemicals. Undirected functionalization of remote aliphatic C–H bonds is a synthetically valuable but largely unknown process. Synergistic combination of metal-catalyzed chainwalking (migration of a double bond along the hydrocarbon chain, a process involving repeated migratory insertions and β-hydride eliminations) and cross-coupling chemistry offers a general approach to the remote functionalization of easily accessed unsaturated hydrocarbon substrates. In this paper, we demonstrate that direct installation of a distal arylamino group can be achieved from two common feedstock chemicals (olefins and nitroarenes) via nickel hydride chemistry. It is anticipated that the strategy could inspire the development of other remote functionalizations with different regioselectivity as well as asymmetric transformations. Zhu and colleagues describe the remote hydroamination of alkenes with nitro(hetero)arenes through nickel-catalyzed alkene isomerization and sequential reductive relay hydroamination process. Using two common feedstock chemicals, olefins and nitroaromatics, in an operationally simple procedure, this attractive protocol provides efficient and practical access to a wide range of arylamines under mild conditions.
Efficient and stereoselective synthesis of allylic ethers and alcohols
Pospisil, Jiri,Marko, Istvan E.
, p. 5983 - 5986 (2007/10/03)
(Chemical Equation Presented) A short and efficient synthesis of allylic TBS ethers and allylic alcohols has been developed, based upon a unique Kocienski-Julia olefination reaction. Allylic alcohols and allylic ethers are obtained in good to excellent yields and with high (E)-selectivity. The conditions are mild and the procedure is broadly applicable.
