Fig. 4: Gram-scale synthesis and further transformation.
From: Carbodefluorination of fluoroalkyl ketones via a carbene-initiated rearrangement strategy
a Gram-scale synthesis and further transformation of compound 3; b Gram-scale synthesis and further transformation of compound 86; c Gram-scale synthesis and further transformation of compound 127. Reaction conditions: a. 3 (0.2 mmol), difluoroacetaldehyde N-triftosylhydrazone (DFHZ-Tfs) (0.4 mmol), FeTPPCl (3 mol%), aqueous NaOH (5.0 wt%)/toluene, 60 °C; b. 3 (0.2 mmol), trifluoroacetaldehyde N-tfsylhydrazone (TFHZ-Tfs) (0.4 mmol), FeTPPCl (3 mol%), K2CO3 (0.6 mmol), 1,4-dioxane (3 mL), 40 °C; c. 3/86/127 (0.2 mmol), NaBH4 (0.24 mmol) in CH3OH (2 mL) at 25 °C; d. NaI (0.32 mmol), TMSCl (0.32 mmol), H2O (0.16 mmol), CH3CN (2 mL), room temperature; e. 3 (0.3 mmol), NBS (1.1 equiv), DCM (2 mL), 0 °C ~ rt; f. 3/86/127 (0.2 mmol), Ph3PCH3Br (0.4 mmol), tBuOK (0.4 mmol), THF (2 mL), 25 °C; g. 3 (0.2 mmol), Ph3PCH3Br (0.3 mmol), tBuOK (0.3 mmol), THF (2 mL), 25 °C ~ 60 °C; h. 86/127/200/205 (0.2 mmol), DAST (0.2 mmol) in DCM (2 mL) at −78 °C ~ rt; i. 86 (0.2 mmol), TolSO2Na (1.8 mmol), CH3COCl (1.2 mmol), CHCl3 (2 mL), 10 °C; j. 127 (0.2 mmol), AIBN (0.04 mmol), ethyl bromomethacrylate (0.4 mmol), toluene (2 mL), 80 °C. Ts tosyl, nBu n-butyl, Tol tolyl, dr diastereomeric ratio.
