19013-30-0Relevant articles and documents
Palladium-Catalyzed Cyclobutanation of Aryl Sulfonates through both C-O and C-H Cleavage
Zhang, Liangwei,Liu, Long,Huang, Tianzeng,Dong, Qizhi,Chen, Tieqiao,Chen, Tieqiao
, p. 2189 - 2196 (2020/06/05)
A palladium-catalyzed cyclobutanation of aryl sulfonates with strained alkenes has been developed. The methodology is featured to achieve the cleavage of both C-O and C-H bonds of phenol derivatives in one pot. Under the reaction conditions, in addition t
Palladium-catalyzed intra-and intermolecular C-H arylation using mesylates: Synthetic scope and mechanistic studies
Ferguson, Devin M.,Rudolph, Stacey R.,Kalyani, Dipannita
, p. 2395 - 2401 (2014/07/21)
This paper describes the development of Pd-catalyzed inter-and intramolecular direct arylation using mesylates. Furthermore, a sequential mesylation/arylation protocol using phenols as substrates is described. These transformations are general with respect to the electronics of the C-H substrates and allow for the synthesis of diverse heterocyclic motifs in good yields. Both arenes and heteroarenes efficiently participate in these reactions. Preliminary mechanistic studies are presented for both inter-and intramolecular arylations.
Mechanistic insight into the formal [1,3]-migration in the thermal claisen rearrangement
Hou, Shili,Li, Xinyao,Xu, Jiaxi
, p. 10856 - 10869 (2013/02/23)
The thermal formal [1,3]-sigmatropic shift of allyl aryl ethers has been studied in depth experimentally with the aid of the density functional theory (DFT) calculations of the B3LYP function. Three mechanistic possibilities, referred to as the radical, ionic, and concerted mechanisms, have previously been put forth to explain the thermal [1,3]-rearrangement process. However, the intercrossing and radical trapping experiments indicate the rearrangement is an intramolecular process. The computational studies reveal that the concerted C[1,3]-sigmatropic shift suffered from a higher energetic barrier to allow the rearrangement to proceed under the conditions used. However, a tandem O[1,3]-sigmatropic shift with a configuration inversion of the oxygen atom and [3,3]-sigmatropic shift (the Claisen rearrangement) is the most likely pathway for the formal [1,3] rearrangement. Furthermore, the rearrangement experiments with a designed optically active substrate and O[1,3]-sigmatropic shift examples verify the new cascade rearrangement. In addition, computational and experimental studies indicate that water molecule assists the proton shift during the isomerization. The combined methods provide the new insight into the mechanism of the thermal formal [1,3]-migration in the Claisen rearrangement and the novel O[1,3]-sigmatropic shift as well.
