52506-24-8Relevant academic research and scientific papers
Silver-Catalyzed N-H Functionalization of Aryl/Aryl Diazoalkanes with Anilines
He, Feifei,Empel, Claire,Koenigs, Rene M.
, p. 6719 - 6723 (2021)
Herein, we report on the N-H functionalization reaction of primary and secondary anilines with diaryldiazoalkanes using simple AgPF6 as catalyst. We demonstrated broad applicability in the reaction of diaryldiazoalkanes with different anilines (31 examples, up to 97% yield). Furthermore, we propose a possible reaction mechanism for the N-H functionalization.
Proton or Carbene Transfer? On the Dark and Light Reaction of Diazoalkanes with Alcohols
Empel, Claire,He, Feifei,Jana, Sripati,Koenigs, Rene M.,Pei, Chao
supporting information, (2022/02/21)
The formal alkylation reaction of OH groups with diazoalkanes under catalyst-free reaction conditions finds broad application in organic synthesis. However, even today, this reaction is mainly limited to the use of diazomethane as reaction partner. In thi
Enantioselective Si-H Insertion Reactions of Diarylcarbenes for the Synthesis of Silicon-Stereogenic Silanes
Jagannathan, Jake R.,Fettinger, James C.,Shaw, Jared T.,Franz, Annaliese K.
supporting information, p. 11674 - 11679 (2020/07/27)
We report the first example of enantioselective, intermolecular diarylcarbene insertion into Si-H bonds for the synthesis of silicon-stereogenic silanes. Dirhodium(II) carboxylates catalyze an Si-H insertion using carbenes derived from diazo compounds where selective formation of an enantioenriched silicon center is achieved using prochiral silanes. Fourteen prochiral silanes were evaluated with symmetrical and prochiral diazo reactants to produce a total of 25 novel silanes. Adding an ortho substituent on one phenyl ring of a prochiral diazo enhances enantioselectivity up to 95:5 er with yields up to 98percent. Using in situ IR spectroscopy, the impact of the off-cycle azine formation is supported based on the structural dependence for relative rates of diazo decomposition. A catalytic cycle is proposed with Si-H insertion as the rate-determining step, supported by kinetic isotope experiments. Transformations of an enantioenriched silane derived from this method, including selective synthesis of a novel sila-indane, are demonstrated.
