# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2003

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A novel route to the fluorinated diimines: carbon monoxide-promoted
reductive homocoupling of fluorinated imidoyl iodides in the presence
of a palladium catalyst

Hideki Amii, Mitsuhiro Kohda, Motoharu Seo and Kenji Uneyama*
Synthesis of the fluorinated diimine 2a (0.5 mmol scale).

A two-necked flask attached a CO (1 atm) balloon was charged Pd2(dba)3•CHCl3 (0.025
g, 0.025 mmol) and K2CO3 (0.138 g, 1 mmol), and toluene(2 mL). Then 0.165 g (0.50
mmol) of trifluoroacetimidoyl iodide 3a in 2 mL of toluene was added to the catalyst
mixture. Subsequently, 0.05 mL of DMF was added. The reaction vessel was wrapped
with aluminum foil to minimize exposure to the light. The reaction mixture was stirred
at 70 °C for 7 h. The reaction was monitored by TLC. When the imidoyl iodide 3a was
consumed, the resulting suspension was filtered through a short celite column (AcOEt).
After evaporation of solvent, the residue was purified by silica gel column
chromatography (hexane : ether (9:1) elute) to give yellow solid of 2a (0.064 g, 0.16
mmol, 64%): Mp 121 oC; IR(KBr) 1598, 1506 cm-1; 1H NMR (CDCl3, 200 MHz) ä 6.78
(s, 8 H), 3.80 (s, 6 H); 19F NMR (CDCl3, 188 MHz, C6F6 as an internal standard) ä 93.9
(s, 6 F); MS m/z 404 (M+ 8), 389 (14), 202 (100), 107 (43), 77 (73). Anal. Calcd for
C18H14F6N2O2: C, 53.47; H, 3.49; N, 6.93. Found: C, 53.28; H, 3.34; N, 7.23.
Compound 2b: yellow solid; Mp 103 oC; IR (KBr) 1604, 1506 cm-1; 1H NMR (200
MHz, CDCl3) ä 7.02 (d, J = 8, 4 H), 6.50 (d, J = 8, 4 H), 2.33 (s, 6 H); 19F NMR (188
MHz, CDCl3) ä 93.9 (s, 6 F); MS m/z 372 (M+ 10), 357 (16), 186 (59), 91 (100), 65 (44).
Anal. Calcd for C18H14F6N2: C, 58.07; H, 3.79; N, 7.52. Found: C, 58.42; H, 3.89; N,
7.45.

Compound 2c: yellow oil; IR (KBr) 1596, 1488 cm-1; 1H NMR (200 MHz, CDCl3) ä
7.2-7.1 (m, 6 H), 6.5-6.4 (m, 4 H); 19F NMR (188 MHz, CDCl3) ä 93.9 (s, 6 F); MS m/z
344 (M+ 100), 172 (95), 77 (93). Anal. Calcd for C16H10F6N2: C, 55.82; H, 2.93; N, 8.14.
Found: C, 55.48; H, 2.76; N, 8.35.

Compound 2d: yellow solid; Mp 121 oC; IR (KBr) 1486 cm-1; 1H NMR (200 MHz,
CDCl3) ä_7.22 (d, J = 9, 4 H), 6.44 (d, J = 9, 4 H); 19F NMR (188 MHz, CDCl3) ä 93.8
(s, 6 F); MS m/z 412 (M+ 28), 377 (20), 206 (100), 111 (90), 75 (46). Anal. Calcd for
C16H8Cl2F6N2: C, 46.51; H, 1.95; N, 6.78. Found: C, 46.70; H, 1.90; N, 6.71.

Compound 2e: red oil; IR (neat) 1680, 1596 cm-1; 1H NMR (200 MHz, CDCl3) ä
6.9-7.0 (brs, 6 H), 2.10 (brs, 6H), 1.56 (brs, 6 H); 19F NMR (188 MHz, CDCl3) ä 95.7 (s,
3 F), 93.5 (s, 3 F); MS m/z 400 (M+ 2), 385 (43), 200 (100), 131 (65), 105 (90), 77 (76).
Anal. Calcd for C20H18F6N2: C, 60.00; H, 4.53; N, 7.00. Found: C, 60.01; H, 4.87; N,
6.79.
Compound 2f: red oil; IR (neat) 1684 cm-1; 1H NMR (200 MHz, CDCl3) ä 7.2-6.9 (brs,
6 H), 2.9-2.6 (brs, 4 H), 1.3-0.8 (brs, 24 H); 19F NMR (188 MHz, CDCl3) ä 98-97 (brs,
3 F), 95-94 (brs, 3 F); MS m/z 512 (M+ 1), 469 (15), 256 (100), 214 (33). Anal. Calcd
for C28H34F6N2: C, 65.61; H, 6.69; N, 5.47. Found: C, 65.70; H, 7.08; N, 5.73.

# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2003

Compound 2g: yellow solid; Mp 115 oC; IR (KBr) 1592, 1508 cm-1; 1H NMR (200
MHz, CDCl3) ä 7.4-7.1 (m, 8 H), 7.0-6.9 (m, 2 H), 6.8-6.6 (m, 4 H); 19F NMR (188
MHz, CDCl3) ä 94.1 (s, 6 F); MS m/z 444 (M+ 75), 375 (66), 222 (57), 202 (94), 127
(100). Anal. Calcd for C24H14F6N2: C, 64.87; H, 3.18; N, 6.30. Found: C, 64.61; H,
3.11; N, 6.27.
Compound 2h: yellow solid; Mp 70 oC; IR (KBr) 1596, 1506 cm-1; 1H NMR (200 MHz,
CDCl3) ä 7.05 (d, J = 9, 4 H), 6.85 (d, J = 9, 4 H), 3.83 (s, 6 H); 19F NMR (188 MHz,
CDCl3) ä 81.7 (t, J = 21, 6 F), 60-58 (m, 2 F), 49-46 (m, 2 F), 37.7 (t, J = 6, 4 F); MS
m/z 604 (M+ 2), 302 (100), 92 (38), 77 (67). Anal. Calcd for C22H14F14N2O2: C, 43.72;
H, 2.33; N, 4.64. Found: C, 43.55; H, 2.48; N, 4.27.
Compound 2i: as a mixture of E/E, Z/Z or E/Z diastereomers. A diastereomer ratio of
9:2 was determined by comparing the intensities of the indicated 19H NMR peaks (*
=major isomer; ** = minor isomer); [á]23
D -4.37 (c 0.79, CHCl3); IR (neat) 1660 cm-1;
1H NMR (200 MHz, CDCl3) ä 6.8-7.4 (m, 10 H), **4.57 (q, J = 6, 2 H), *4.19 (q, J = 6,
2 H), **1.63 (d, J = 6, 6 H), *1.39 (d, J = 6, 6 H); 19F NMR (188 MHz, CDCl3) ä **92.0
(s, 6 F), *91.9 (s, 6 F); MS m/z 400 (M+ 1), 295 (15), 281 (12), 105 (100). Anal. Calcd
for C20H18F6N2: C, 60.00; H, 4.53; N, 7.00. Found: C, 60.28; H, 4.32; N, 6.85.

Synthesis of the fluorinated diimine 2a (10 mmol scale).
A two-necked flask attached a CO (1 atm) balloon was charged Pd2(dba)3•CHCl3 (0.522
g, 0.506 mmol) and K2CO3 (2.81 g, 20.3 mmol), and toluene(10 mL). Then 3.31 g (10.1
mmol) of trifluoroacetimidoyl iodide 3a in 10 mL of toluene was added to the catalyst
mixture. Subsequently, 1.0 mL of DMF was added. The reaction vessel was wrapped
with aluminum foil to minimize exposure to the light. The reaction mixture was stirred
at 70 °C overnight. When the imidoyl iodide 3a was consumed, the resulting suspension
was filtered through a short celite column (AcOEt). After evaporation of solvent, the
residue was purified by silica gel column chromatography (hexane : ether (9:1) elute) to
give yellow solid of 2a (1.29 g, 3.19 mmol, 63%).