diastereoselective radical 1,5 phenylmigration reactions fromsilicon in diarylsilyl ethers to various C-centered radicals to form the corresponding 3-phenylated alcohols are described. Functionalized aryl groups can also be transferred. The effect of the variation of the attacking radical on the aryl transfer reaction is discussed. Best results are obtained for the phenylmigration to nucleophilic secondary
Dichotomy of Manganese Catalysis via Organometallic or Radical Mechanism: Stereodivergent Hydrosilylation of Alkynes
作者:Xiaoxu Yang、Congyang Wang
DOI:10.1002/anie.201710206
日期:2018.1.22
Herein, we disclose the first manganese‐catalyzed hydrosilylation of alkynes featuring diverse selectivities. The highly selective formation of E‐products was achieved by using mononuclear MnBr(CO)5 with the arsenic ligand, AsPh3. Whereas using the dinuclear catalyst Mn2(CO)10 and LPO (dilauroyl peroxide) enabled the reversed generation of Z‐products in good to excellent stereo‐ and regioselectivity