704-43-8Relevant articles and documents
Design, Synthesis, and Implementation of Sodium Silylsilanolates as Silyl Transfer Reagents
Yamagishi, Hiroki,Saito, Hayate,Shimokawa, Jun,Yorimitsu, Hideki
, p. 10095 - 10103 (2021/08/18)
There is an increasing demand for facile delivery of silyl groups onto organic bioactive molecules. One of the common methods of silylation via a transition-metal-catalyzed coupling reaction employs hydrosilane, disilane, and silylborane as major silicon sources. However, the labile nature of the reagents or harsh reaction conditions sometimes render them inadequate for the purpose. Thus, a more versatile alternative source of silyl groups has been desired. We hereby report a design, synthesis, and implementation of storable sodium silylsilanolates that can be used for the silylation of aryl halides and pseudohalides in the presence of a palladium catalyst. The developed method allows a late-stage functionalization of polyfunctionalized compounds with a variety of silyl groups. Mechanistic studies indicate that (1) a nucleophilic silanolate attacks a palladium center to afford a silylsilanolate-coordinated arylpalladium intermediate and (2) a polymeric cluster of silanolate species assists in the intramolecular migration of silyl groups, which would promote an efficient transmetalation.
Sterically facilitated meta-lithiation of arenes, containing electron-donating groups
Antonov, Alexander S.,Bardakov, Victor G.,Mulloyarova, Valeriia V.
supporting information, (2019/12/11)
The influence of the bulky trimethylsilyl substituent on the selectivity of metallation of dimethylaniline, anisole and 1-dimethylaminonaphthalene is studied. The neighboring SiMe3 group forces dimethylamino and methoxy groups to occupy a confo
Direct ortho Arylation of Anisoles via the Formation of Four-Membered Lithiumcycles/Palladacycles
Xiong, Xiaoyu,Zhu, Ranran,Huang, Lin,Chang, Shuqin,Huang, Jianhui
supporting information, p. 2046 - 2050 (2017/09/13)
We report here our latest discovery on the directed lithiation and palladium-catalyzed arylation of anisoles. During this research, the formation of a four-membered lithiumcycle followed by transmetalation to the corresponding palladacycle has been achieved, which is difficult to be obtained from palladium-catalyzed C-H activation processes. This approach has provided an alternative way of introducing functionalities to arenes such as anisoles, thioanisoles, and anilines. This approach also features an excellent monoselectivity compared with reactions under transition-metal-catalyzed conditions.