F. Nmr, CDCl 3 ): ? -108.7 (q app ) ? -119

F. Nmr, CDCl 3 ): ? -108.1 (q app ) ? -118

. Anal, Calcd for C 21 H 27 FO 2 Si: C, 70.35; H, 7.59. Found: C, 70.52, pp.7-75

=. Mw, 52 g.mol -1 C 21 H 27 FO 2 Si Yield = 87 % (E/Z: 35/65) R f = 0, PE/EtOAc: 90/10) Colorless oil Experimental Section 2) Diastereoselective Electrophilic Addition

F. Nmr, CDCl 3 ): ? -107.5 (q app ) ? -116

C. Hz, 61.6 (d, 2 J C5Z-F = 35.6 Hz, pp.100-107

. Anal, Calcd for C 21 H 25 FO 3 Si: C, 67.71; H, 6.76. Found: C, 67.77, pp.6-81

=. Mw, 51 g.mol -1 C 21 H 25 FO 3 Si Yield = 71% (E/Z: 35/65) Colorless oil Experimental Section 2) Diastereoselective Electrophilic Addition The crude mixture was purified by column chromatography on silica gel

. Anal, Calcd for C 23 H 29 FO 3 Si: C, 68.97

C. Hz, 1 (d, 4 J C3-F = 1.6 Hz, C3), 104.6 (d, 2 J C1-F = 13, p.6

. Anal, Calcd for C 20 H 18 FNO 4 : C, 67.60; H, 5.11; N, 3.94 Found: C, 67.35; H, 4.78

. Anal, Calcd for C 19 H 19 FO 2 : C, 76.49; H, 6.42. Found: C, 76.52, pp.6-55

. Anal, Found: 63.44; H, 8.37; N, 4.11; S, 9.40. Compound (Z)-75: N-[(Z)-1-(3-aminopropyl)-2-fluoro-3-(4-methoxyphenyl)-2- propenyl]-2-methyl-2-propanesulfinamide To a solution of (Z)-77 in THF were added supported PPh 3 (466 mg, 0.708 mmol, 4 eq.) and H 2 O (100 µL), The reaction mixture was stirred for 40 h and the filtered and concentrated under reduced pressure to afford (Z)-75 as colorless oil

C. Hz, 130.1 (d, 4 J C4-F = 7.7 Hz, C4)

=. Mw, 79 g.mol -1 C 28 H 42 FNO 3 SSi Yield = 86 % R f = 0.23 (DCM/MeOH: 97/3) Colorless oil Experimental Section 3) Fluorinated Syntheses Dipeptides

2. Hz, 80 (s, 3H, H 7 ), 3.87-4.01 (m, 1H, H 8 ), 5.67 (d, 3 J H2-F = 39.2 Hz, 1H, pp.7-43, 2005.

C. Hz, 130.2 (d, 4 J C4-F = 7.1 Hz, C4)

=. Mw, 79 g.mol -1 C 17 H 25 FN 4 O 2 S Yield = 50 % over 2 steps R f = 0.23 (EP/EtOAc: 60/40) Colorless oil Experimental Section 3) Fluorinated Syntheses Dipeptides

. Anal, Calcd for C 30 H 29 FN 4 O 4 : C, 68.17; H, 5.53; N, 10.60. Found: C, 68.32; H, 5.70; N, 10

. Anal, Found: C, 60.20; H, 7.64; N, 3.52; S, 3.04 Compound 93: iodomethylpivalate A solution of freshly distilled chloromethyl pivalate (1.44 mL, 9.9 mmol, 1 eq.) and sodium iodide (3.58 g, 23.9 mmol, 2.4 eq.) in acetone (10 mL) was stirred for 3 h at 25°C. GC analysis showed the completion of the reaction and hexane was added (35 mL) The reaction mixture was filtered through a pad of celite® and the filtrate was washed

. Anal, 89; H, 6.63; N, 3.54; S. Found: C, 73.21; H, 6.94; N, 3.57, ? (Z)-104 diastereomer 2.62 (m, 2H, H 3 ), 3.56 (br s, 1H, OH), 4.21 (t, pp.4-37

. Anal, Calcd for C 24 H 22 FNO: C, 70.40; H, 5.91; N, 3.42; S. Found: C, 70.48; H, 6.00; N, 3.45

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