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4l as a white solid; yield: 95 mg (78% with 1) and 97 mg
(80% with 2); mp 61–638C. 1H NMR (CDCl3, 400 MHz):
d=4.48–4.39 (m, 1H), 3.89–3.71 (m, 2H), 3.11–2.92 (m,
1H), 2.87–2.66 (m, 1H), 2.12 (t, J=6.4 Hz, 1H); 13C NMR
(CDCl3, 101 MHz): d=68.1, 37.6 (t, J=21.3 Hz), 21.9; HR-
MS (ESI): m/z=602.9082, calcd. for C11H5F17IO: 602.9108.
Compound 4m: Synthesized from 1 (0.73 mg, 0.001 mmol)
a yellow oil; yield: 72 mg (77% with 1) and 74 mg (80%
with 2). H NMR (CDCl3, 400 MHz): d=6.48 (t, J=14.4 Hz,
1
1H, E), 6.39 (t, J=13.2 Hz, 0.4H, Z), 3.89–3.78 (m, 2.8H,
E+Z), 3.04–2.84 (m, 2.8H, E+Z), 1.89 (brs, 1.4H, E+Z);
13C NMR (CDCl3, 101 MHz): E d=129.3 (t, J=24.03 Hz),
117.2, 62.0, 43,7; Z d=124.6 (t, J=23.9 Hz), 120.3, 60.7,
51.0; EI-MS: m/z (relative intensity)=466 (M, 30), 120
+
or
2
(0.36 mg, 0.002 mmol), prop-2-en-1-ol (13.6 mL,
(C5H6F2O+, 68), 69 (CF3 , 100).
0.2 mmol) and 1,1,1,2,3,3,4,4-octafluoro-4-iodo-2-(trifluoro-
methyl)butane (46.5 mL, 0.24 mmol) in CD3OD (1 mL). The
residue was purified by flash chromatography over silica gel
(pentane/EtOAc, 90/10) to afford 4m as a yellow oil; yield:
73 mg (80% with 1) and 66 mg (73% with 2). 1H NMR
(CDCl3, 400 MHz): d=4.48–4.37 (m, 1H), 3.90–3.72 (m,
2H), 3.11–2.91 (m, 1H), 2.87–2.67 (m, 1H), 2.16 (t, J=
6.4 Hz, 1H); 13C NMR (CDCl3, 101 MHz): d=68.1, 37.7 (t,
J=21.4 Hz), 22.0; EI-MS: m/z (relative intensity)=327
Compound 5c: Synthesized from 1 (0.73 mg, 0.001 mmol)
or
2
(0.36 mg, 0.002 mmol), prop-2-yn-1-ol (11.5 mL,
0.2 mmol) and C8F17I (218.4 mg, 0.4 mmol) in CD3OD
(1 mL). The residue was purified by flash chromatography
over silica gel (pentane/EtOAc, 90/10, v/v) to afford the 5c
(E:Z=1:1.6) as a white solid; 68 mg (57% with 1) and
83 mg (69% with 2); mp 60–628C. 1H NMR (CDCl3,
400 MHz): d=6.80 (t, J=13.2 Hz, 0.55H, Z), 6.47 (t, J=
14.8 Hz, 0.35H, E), 4.35 (s, 2H, E+Z), 2.46 (brs, 0.55H, Z),
2.21 (brs, 0.35H, E); 13C NMR (CDCl3, 101 MHz): Z d=
120.1 (t, J=24.1 Hz), 114.4, 72.7; E d=127.5 (t, J=25.0 Hz),
115.8, 65.0; EI-MS: m/z (relative intensity)=602 (M, 5), 475
+
+
(MꢀI, 78), 128 (HI, 78), 69 (CF3 , 100), 57 (C4H9 , 67), 43
+
(C3H7 , 48).
Compound 4n: Synthesized from 1 (0.73 mg, 0.001 mmol)
+
or
2
(0.36 mg, 0.002 mmol), prop-2-en-1-ol (13.6 mL,
(MꢀI, 10), 106 (C4H4F2O+, 100), 69 (CF3 , 40).
0.2 mmol) and C4F9I (41.3 mL, 0.24 mmol) in CD3OD
(1 mL). The residue was purified by flash chromatography
over silica gel (pentane/EtOAc, 85/15) to afford 4n as
a yellow oil; yield: 65 mg (79% with 1) and 53 mg (65%
Compound 5d: Synthesized from a mixture of complex
1 (0.73 mg, 0.001 mmol) or 2 (0.36 mg, 0.002 mmol), prop-2-
yn-1-ol (11.5 mL, 0.2 mmol) and 1,1,1,2,3,3,4,4-octafluoro-4-
iodo-2-(trifluoromethyl)butane (77.5 mL, 0.4 mmol) in
CD3OD (1 mL). The residue was purified by flash chroma-
tography over silica gel (pentane/EtOAc, 80/20, v/v) to
afford 5d (E:Z=1:1.6) as a yellow oil; yield: 63 mg (70%
with 1) and 66 mg (73% with 2). 1H NMR (CDCl3,
400 MHz): d=6.82 (t, J=13.6 Hz, 1H, Z), 6.50 (t, J=
14.8 Hz, 0.7H, E), 4.36 (s, 3.4H, E+Z), 2.50 (brs, 1H, Z),
2.24 (brs, 0.7H, E); 13C NMR (CDCl3, 101 MHz): Z d=
120.3 (t, J=24.1 Hz), 114.4, 72.7; E d=127.5 (t, J=25.0 Hz),
116.7, 65.0; EI-MS: m/z (relative intensity)=452 (M, 20),
1
with 2). H NMR (CDCl3, 400 MHz): d=4.43 (qt, J=5.2 Hz,
1H), 3.85–3.74 (m, 2H), 3.10–2.91 (m, 1H), 2.86–2.67 (m,
1H), 2.15 (brs, 1H); 13C NMR (CDCl3, 101 MHz): d=68.1,
37.5 (t, J=21.2 Hz), 21.8; EI-MS: m/z (relative intensity)=
+
404 (M, 3); 277 (MꢀI, 100), 128 (HI, 88), 69 (CF3 , 65), 57
+
+
(C4H9 , 80), 43 (C3H7 , 35).
Compound 4o: Synthesized from 1 (0.73 mg, 0.001 mmol)
or
2
(0.36 mg, 0.002 mmol), pent-4-en-1-ol (20.5 mL,
0.2 mmol) and C8F17I (131 mg, 0.24 mmol) in CD3OD
(1 mL). The residue was purified by flash chromatography
over silica gel (pentane/EtOAc, 80/20) to afford 4o as
a yellow solid; yield: 116 mg (92% with 1) and 102 mg (80%
+
325 (MꢀI, 27), 128 (HI, 51),106 (C4H4F2O+, 100), 69 (CF3 ,
52).
Compound 5e: Synthesized from 1 (0.73 mg, 0.001 mmol)
1
with 2); mp 61–638C; H NMR (CDCl3, 400 MHz): d=4.43–
or
2
(0.36 mg, 0.002 mmol), dodec-1-yne (42.75 mL,
4.31 (m, 1H), 3.69 (t, J=6.4 Hz, 2H), 3.03–2.67 (m, 2H),
1.98–1.77 (m, 2H), 1.75–1.60 (m, 1H); 13C NMR (CDCl3,
101 MHz): d=61.7, 41.9 (t, J=20.9 Hz), 37.0, 32.8, 20.3; EI-
0.2 mmol) and C8F17I (218.4 mg, 0.4 mmol) in CD3OD
(1 mL). The residue was purified by flash chromatography
over silica gel (100% pentane) to afford 5e (E:Z=2.4:1) as
a yellow oil; yield: 114 mg (80% with 1) and 134 mg (94%
+
ꢀ
MS: m/z (relative intensity)=505 (M I, 20), 379 (C13H8F17
,
+
+
1
40), 73 (C4H9O+, 100), 69 (CF3 , 70), 57 (C4H9 , 55).
with 2). H NMR (CDCl3, 400 MHz): d=6.34 (t, J=14.4 Hz,
Compound 5a: Synthesized from 1 (0.73 mg, 0.001 mmol)
(0.36 mg, 0.002 mmol), but-3-yn-1-ol (15.1 mL,
1H, E), 6.39 (t, J=13.2 Hz, 0.25H, Z), 2.77–2.57 (m, 2.5H,
E+Z), 1.67–1,52 (m, 2.5H, E+Z), 1.31–1,19 (m, 17.5H,
E+Z), 0.88 (t, J=6.4 Hz, 3.75H, E+Z); 13C NMR (CDCl3,
101 MHz): E d=126.7 (t, J=24.03 Hz), 123.3, 41.3, 32.1,
29.7, 29.5, 29.4, 28.6, 22.9, 14.2; Z d=123.2, 121.8 (t, J=
23.93 Hz), 48.6, 32.1, 29.7, 29.5, 29.2, 28.2, 22.9, 14.2; EI-MS:
m/z (relative intensity)=712 (M, 2), 585 (MꢀI, 2), 529
or
2
0.2 mmol) and C8F17I (218.4 mg, 0.4 mmol) in CD3OD
(1 mL). The residue was purified by flash chromatography
over silica gel (pentane/EtOAc, 90/10, v/v) to afford 5a
(E:Z=2.7:1) as a white solid; yield: 98 mg (79% with 1) and
102 mg (77% with 2); mp 65–678C. 1H NMR (CDCl3,
400 MHz): d=6.48 (t, J=14.0 Hz, 0.65H, E), 6.40 (t, J=
13.2 Hz, 0.31H, Z), 3.90–3.80 (m, 2H, E+Z), 3.02–2.87 (m,
2H, E+Z), 1.69 (brs, 1H, E), 1.25 (brs, 0.4H, Z); 13C NMR
(CDCl3, 101 MHz): E d=129.2 (t, J=23.8 Hz), 117.2, 62.0,
43,8; Z d=124.5 (t, J=23.8 Hz), 118.7, 60.7, 51.1; HR-MS
(ESI): m/z=614.9105, calcd. for C12H5F17IO: 614.9108.
+
(MꢀC4H8I+, 10), 97 (C7H13+, 50), 83 (C6H11+, 60), 57 (C4H9 ,
+
90), 43 (C3H7 , 100).
Compound 5f: Synthesized from 1 (0.73 mg, 0.001 mmol)
or
2
(0.36 mg, 0.002 mmol), dodec-1-yne (42.75 mL,
0.2 mmol) and 1,1,1,2,3,3,4,4-octafluoro-4-iodo-2-(trifluoro-
methyl)butane (77.5 mL, 0.4 mmol)) in CD3OD (1 mL). The
residue was purified by flash chromatography over silica gel
(100% pentane) to afford 5f (E:Z=3.2:1) as a yellow oil;
yield: 95 mg (85% with 1) and 784 mg (75% with 2).
1H NMR (CDCl3, 400 MHz): d=6.32 (t, J=14.4 Hz, 1H, E),
6.24 (t, J=12.8 Hz, 0.25H, Z), 2.76–2.53 (m, 2.5H, E+Z),
1.70–1,51 (m, 2.5H, E+Z), 1.43–1,15 (m, 17.5H, E+Z),
Compound 5b: Synthesized from 1 (0.73 mg, 0.001 mmol)
or
2
(0.36 mg, 0.002 mmol), but-3-yn-1-ol (15.1 mL,
0.2 mmol) and 1,1,1,2,3,3,4,4-octafluoro-4-iodo-2-(trifluoro-
methyl)butane (77.5 mL, 0.4 mmol) in CD3OD (1 mL). The
residue was purified by flash chromatography over silica gel
(pentane/EtOAc, 80/20, v/v) to afford 5b (E:Z=3:1) as
Adv. Synth. Catal. 0000, 000, 0 – 0
11
ꢂ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
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