101224-30-0Relevant articles and documents
Nickel-Catalyzed Csp2-Csp3 Bond Formation via C-F Bond Activation
Ho, Yee Ann,Leiendecker, Matthias,Liu, Xiangqian,Wang, Chengming,Alandini, Nurtalya,Rueping, Magnus
, p. 5644 - 5647 (2018)
A nickel-catalyzed cross coupling of aryl fluorides via C-F bond activation has been developed. The alkylation method allows selective replacement of aryl fluorides by alkyl groups and enables the synthesis of diverse and otherwise difficult to access scaffolds in good yields.
Competing pathways in the photogeneration of didehydrotoluenes from (Trimethylsilylmethyl)aryl sulfonates and phosphates
Crespi, Stefano,Ravelli, Davide,Protti, Stefano,Albini, Angelo,Fagnoni, Maurizio
supporting information, p. 17572 - 17578 (2015/02/18)
The scope of the photochemical generation of a,n-didehydrotoluene diradicals from aryl sulfonates and phosphates and their chemistry are explored. The thermally inaccessible a,2- and a,4-intermediates are efficiently obtained by irradiation of ortho- and para-(trimethylsilylme-thyl)phenyl triflates through heterolytic splitting of the ester anion from the substrate in the triplet state. Triplet phenyl cations are formed and the loss of trimethylsilyl cation from them affords the desired diradicals (3Me3SiCH2C6H4-OZ→ 3Me3SiCH2C6H4+→CH2C6H4). Triplet sensitization is required, for which acetone is used throughout. Direct irradiation leads, on the contrary, to photo-Fries fragmentation (1Me3SiCH2C6H4O-Z→Me3SiCH2C6H4O· + Z). With mesylates, where ester cleavage is less convenient, a further competition from the triplet is direct desilylation. Didehydrotoluenes are also obtained from the corresponding phosphates, although with poor efficiency.
