Synthesis of α-fluoroketones and α-fluoroenones in aqueous media

Synthesis of α‐Fluoroketones by Insertion of HF into a Gold Carbene

“…It can be simply reduced by NaBH 4 to give the fluorohydrin 4 in quantitative yield . 3 can also react with aldehyde to give the aldol condensation product 5 (fluorinated α,β‐unsaturated ketone) . Reaction of 3 with a Michael acceptor gives the 1,4‐addition product 6 via an enamine intermediate .…”

Site‐Selective Tertiary Alkyl–Fluorine Bond Formation from α‐Bromoamides Using a Copper/CsF Catalyst System

“…In this case, 2 g and 2 h are considered to form by an S N 2 reaction. [9] The p-anisylsubstituted substrate gave 2 f in good yield, thus illustrating that substrates with tertiary alkyl-Br bonds and N-arylsubstituted amides reacted smoothly with CsF in the presence of a copper catalyst. In contrast, N-alkyl-substituted tertiary amides, such as the substrate leading to 2 i, were not reactive.…”

“…For example, primary and secondary alkyl-F bonds formed in the presence of CsF in yields of 47 and 14 %, respectively, [9] but tertiary alkyl-F bonds did not form (Scheme 1).…”

Synthesis of α‐Fluoroketones by Insertion of HF into a Gold Carbene

“…[26] 3 can also react with aldehyde to give the aldol condensation product 5 (fluorinated a,b-unsaturated ketone). [27] Reaction of 3 with aM ichael acceptor gives the 1,4-addition product 6 via an enamine intermediate. [28] And reductive amination of 3 gives the b-fluoroamine 7 in good yield.…”