7022-45-9Relevant articles and documents
Rhodium(III)-Catalyzed Aldehyde C?H Activation and Functionalization with Dioxazolones: An Entry to Imide Synthesis
Bellière-Baca, Virginie,Clavier, Hervé,Hérault, Damien,Massouh, Joe,Petrelli, Antoine
supporting information, (2022/01/06)
A rhodium(III)-based catalytic system has been used to develop a C?H bond activation of benzaldehyde derivatives and subsequent functionalization with dioxazolones in order to afford imides. The importance of the nature of the directing group to perform selectively the aldehydic C?H bond activation has been highlighted. The scope investigation showed that this transformation could be applied to various dioxazolones and many benzaldehyde derivatives as well as an acrolein derivative. Derivatization reactions of the imide products demonstrated the synthetic utility of this rhodium-catalyzed aldehydic C?H amidation.
Unexpected formation of 4,7-dihalobenzo[b]thiophenes using Ohira-Bestmann reagent and reactivity of the halogen-substituted benzo[b]thiophenes in Suzuki-Miyaura coupling with phenylboronic acid
Toyota, Kozo,Mutoh, Hirotaka,Kishi, Hiroki,Mikami, Shinichi,Tanaka, Hiroki,Yoshida, Shuhei,Naganuma, Daisuke
, p. 1355 - 1374 (2019/12/23)
Reaction of 2-(1-adamantylsulfanyl)-3,6-dihalobenzaldehydes with Ohira-Bestmann reagent gave 4,7-dihalobenzo[b]thiophenes along with normal alkyne products. Nine types of 4,7-dihalobenzo[b]thiophenes bearing chlorine, bromine, or iodine atoms, were prepared by this method. Regioselectivity in Suzuki-Miyaura cross coupling reactions of the 4,7-dihalobenzo[b]thiophenes with PhB(OH)2 was also studied.
The Key Role of the Nonchelating Conformation of the Benzylidene Ligand on the Formation and Initiation of Hoveyda-Grubbs Metathesis Catalysts
Bieszczad, Bartosz,Barbasiewicz, Micha?
supporting information, p. 10322 - 10325 (2015/07/07)
Experimental studies of Hoveyda-Grubbs metathesis catalysts reveal important consequences of substitution at the 6-position of the chelating benzylidene ligand. The structural modification varies conformational preferences of the ligand that affects its exchange due to the interaction of the coordinating site with the ruthenium center. As a consequence, when typical S-chelated systems are formed as kinetic trans-Cl2 products, for 6-substituted benzylidenes the preference is altered toward direct formation of thermodynamic cis-Cl2 isomers. Activity data and reactions with tricyclohexylphosphine (PCy3) support also a similar scenario for O-chelated complexes, which display fast trans-Cl2?cis-Cl2 equilibrium observed by NMR EXSY studies. The presented conformational model reveals that catalysts, which cannot adopt the optimal nonchelating conformation of benzylidene ligand, initiate through a high-energy associative mechanism.