81245-50-3Relevant articles and documents
Formation of trisubstituted buta-1,3-dienes and α,β-unsaturated ketonesviathe reaction of functionalized vinyl phosphates and vinyl phosphordiamidates with organometallic reagents
Dvo?áková, Hana,Koudelka, Jakub,Oeser, Petr,Tobrman, Tomá?
, p. 35109 - 35120 (2020/10/19)
We studied the reactions of vinyl phosphates and vinyl phosphordiamidates containing an ester functional group with organometallic reagents. We found that the functionalized vinyl phosphates were smoothly converted into tri- and tetrasubstituted buta-1,3-
Selective arylation and vinylation at the α position of vinylarenes
Zou, Yinjun,Qin, Liena,Ren, Xinfeng,Lu, Yunpeng,Li, Yongxin,Zhou, Jianrong
supporting information, p. 3504 - 3511 (2013/07/05)
In intermolecular Heck reactions of styrene and vinylarenes, the aryl and vinyl groups routinely insert at the β position. However, selective insertion at the α position has been very rare. Herein, we provide a missing piece in the palette of Heck reaction, which gave >20:1 α selectivity. The key to our success is a new ferrocene 1,1′-bisphosphane (dnpf) that carries 1-naphthyl groups. Our mechanistic studies revealed that the high α selectivity is partly attributable to the steric effect of dnpf. The rigid and bulky 1-naphthyl groups of dnpf sterically disfavor β insertion. What the Heck! In intermolecular Heck reactions, insertion at the β position of aromatic olefins is very common, but reversal of the selectivity for selective α insertion has been a longstanding problem. A general method to couple aryl and vinyl triflates with aromatic olefins in >20:1 α selectivity is presented. The key to this successful approach is a new ferrocene bisphosphane with naphthyl groups on the phosphorus atom (see scheme; OTf=triflate). Copyright
