A variety of γ‐amino‐α,β‐unsaturated amides have been synthesized from readily available α‐fluoroenamides precursors via an unprecedented intermolecular and intramolecular conjugative catalytic amination process. These γ‐amino‐α,β‐unsaturated amides are useful intermediates for accessing rarely synthesized hybrid peptides, αγα sequences, and various classes of alkaloids containing a pyrrolidine ring, as illustrated by total synthesis of the indolizidine alkaloid coniceine.

General Methods and Materials 2 General Procedure for α-fluoro-β,γ-unsaturated amides 2 Procedure for Dehydroxyfluorination of α-hydroxy-β,γ-unsaturated 2 Procedure for cross metathesis of allylic fluoride 2 Characterization of the Products 2-9 NMR Spectra of Products 10-Experimental Section General Methods and Materials All reactions were conducted under an argon atmosphere and oven flamed glassware was used. Methylene chloride was distilled over calcium hydride under a nitrogen atmosphere. All other solvents and commercially available reagents were used as received. Reactions were monitored by TLC performed using 0.25 mm E. Merck 5735 Kiegelsel silica gel coated aluminum plates (60F254) using UV radiation (254 nm) as visualizing agent and using solutions of p-anisaldehyde-sulfuric acid-acetic acid in EtOH or KMnO 4-K 2 CO 3 in water followed by heating as developing agent. Flash column chromatography was carried out under pressure on Merck silica gel 40-60 mesh. 1 H NMR and 13 C NMR spectra were recorded at 25 °C on a Brucker Avance 300 MHz (1 H), 282 MHz (19 F) and 75 MHz (13 C), and calibrated using solvent as internal standard (1 H: CDCl 3 7.26 ppm; 13 C CDCl 3 77.16 ppm). Splitting patterns are abbreviated as follows: singlet (s), doublet (d), triplet (t), quartet (q), multiplet (m), broad (br), or a combination of these. IR spectra were recorded on a Perkin Elmer Spectrum 100 FT-IR spectrometer using a ZnSe plate (ATR). High resolution mass spectra (HRMS) were recorded on a Thermo Finnigan MAT95XP and accurate to ± 0.001. I-Procedure for Dehydroxyfluorination of α-hydroxy-β,γ-unsaturated amide. A solution of Deoxo-Fluor (1.5 mmol, 1.5 equiv., 50% in THF) was added to a solution of 1 (1 mmol, 1 equiv.) in CH 2 Cl 2 (4 mL) at-78 °C placed in a round-bottom flask. After addition the solution was mixed at-78 °C for 1 h and the progress of the reaction was monitored by T.L.C. The reaction was allowed to cool to r.t and was then worked up by adding saturated. aqueous NaHCO 3 solution. The product was extracted into CH 2 Cl 2 (3 x 10 mL). The combined organic phases were washed with brine, dried over MgSO 4 , filtered, and concentrated under reduced pressure. The crude was purified over silica gel to give the fluoroolefin 2. II-General Procedure for Deconjugative Electrophilic Fluoration of γ-Silyl Butenamides A solution of allyltrimethylsilane 3a-o (1 equiv.) and Selectfluor (1.5 equiv.) in Acetonitrile (0.2M) was heated to reflux under argon. After completion, reaction was quenched with saturated aqueous NH 4 Cl solution and extracted with EtOAc. The combined organic phases were washed with brine, dried over MgSO 4 , filtered and concentrated under reduced pressure. The crude was purified over silica gel to give the products 4a-o. III-Procedure for Cross Metathesis of allylic fluoride. In a flask, allylic fluoride 4 (0.5 mmol, 1equiv.) was dissolved in dry CH 2 Cl 2 (5 ml). Then 1-hexadecene (0.75 mmol, 1.5 equiv.) and 2 nd generation Hoveyda-Grubbs catalyst (7 mol%) were added and the reaction mixture was stir...