Fluoride ion induced reactions of organocilanes with saturated lactones and αβ-enones

Pd‐Catalyzed Modifiable Silanol‐Directed Aromatic CH Oxygenation

“…Fluoride‐free Hiyama–Denmark cross‐coupling of 9 with phenyl iodide, under conditions reported by Yoshida and co‐workers,18 afforded diarylmethane derivative 11 in 65 % yield. Moreover, fluorosilane 9 in the presence of CsF can be employed as an equivalent of Grignard reagent in the reaction with aldehydes 19. Finally, an unprecedented transformation en route to nitrone derivative 13 was discovered upon treatment of benzylsilane 9 with nitrosobenzene in the presence of CsF 12…”

“…Moreover, fluorosilane 9 in the presence of CsF can be employed as an equivalent of Grignard reagent in the reaction with aldehydes. [19] Finally, an unprecedented transformation en route to nitrone derivative 13 was discovered upon treatment of benzylsilane 9 with nitrosobenzene in the presence of CsF. [12] In summary, Pd-catalyzed benzylsilanol-directed ortho C À H oxygenation of aromatic rings was developed.…”

Novel Isomerization Reaction of N,N-Dimethyl-α-(methoxycarbonyl)-4-substituted- benzylammonium N-Methylides

“…The use of an equimolar amount of cesium fluoride gave 16a (30%) and methyl 2-(dimethylamino)-3-phenyl-3-(trimethylsilyl)propionate ( 21 , 8%), which is a Stevens rearrangement product of ylide 20 . When isolated 21 was stirred in a suspension of cesium fluoride in DMF at room temperature, it was desilylated to 16a in 85% yield …”

Autocatalytic Carbonyl Arylation through In Situ Release of Aryl Nucleophiles from N‐Aryl‐N′‐Silyldiazenes

“…Moreover, modification of the reaction setup with a higher loading of Me 3 SiOK (20 mol %) and slow addition of the diazene (3 equiv) to a solution of a methyl benzoates 8 and THF even enabled two‐fold aryl transfer to give the tertiary silyl ethers 9 in reasonable yields (Scheme , bottom). To the best of our knowledge, this is an unprecedented catalytic arylation of unactivated carboxylic acid derivatives with non‐stabilized carbanion equivalents . We note here that the occurrence of this nucleophilic addition is also diagnostic of the in situ formation of highly reactive aryl anions …”