The Journal of Organic Chemistry
Page 10 of 14
1
2
3
4
5
6
5.54; N, 11.00, S, 12.64; HPLC (CHIRALPAK OD, i-PrOH/ Hexane = 10/90, Flow rate 0.8 mL/
min, λ = 247 nm): t (major) = 16.88 min, t (minor) = 12.06 min, er = 81:19.
7
8
2-(2-chlorophenyl)-2-(6,7-dihydrothieno[3,2-c]pyridin-5(4H)-yl) acetonitrile (4g).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
o
79 mg, 92% yield, white solid (amorphous); mp 123-125 C; 1H NMR (500 MHz, CDCl3): δ
7.66-7.61 (m, 1H), 7.39-7.29 (m, 3H), 6.62 (d, J = 12.5 Hz, 1H), 5.25 (s, 1H), 3.70 (d, J = 15.5
Hz, 1H), 3.55 (d, J = 15.5, 1H), 2.95-2.84 (m, 4H); 13C NMR (125 MHz, CDCl3); δ 134.6, 133.0,
132.5, 130.9, 130.6, 130.1, 126.9, 125.1, 123.1, 115.2, 59.3, 49.5, 47.8, 25.6; [α]D30 = +30.7 (c =
0.030 in isopropanol); TOF–MS (ESI+); m/z calcd. for C15H13ClN2S (M+1) 289.05, Found:
289.00; Anal. Calcd. For C15H13ClN2S: C, 62.38; H, 4.54; N, 9.70, S, 11.10. Found: C, 62.35; H,
4.56; N, 9.71, S, 11.13; HPLC (CHIRALPAK OD, i-PrOH/ Hexane = 10/90, Flow rate 0.8 mL/
min, λ = 247 nm): t (major) = 8.36 min, t (minor) = 7.76 min, er = 78:22.
2-(6,7-dihydrothieno[3,2-c]pyridin-5(4H)-yl)-2-(2-fluorophenyl) acetonitrile (4h).
1
75 mg, 92% yield, white solid (amorphous); mp 92-94 oC; H NMR (500 MHz, CDCl3): δ 7.62
(t, J = 7.5 Hz, 1H), 7.45-7.41 (m, 1H), 7.13 (t, J = 9.25 Hz, 1H), 7.09 (d, J = 5.5 Hz, 1H), 6.71
(d, J = 5.0 Hz, 1H), 5.28 (s, 1H), 3.77 (d, J = 14.0 Hz, 1H), 3.68 (d, J = 14.0 Hz, 1H), 3.02-2.96
13
(m, 3H), 2.91- 2.86 (m, 1H); C NMR (125 MHz, CDCl3); δ 162.9, 160.9, 134.2, 133.9, 132.7,
30
131.5, 126.5, 125.6, 124.6, 117.5, 116.5, 57.3, 51.0, 49.3, 27.0; [α]D = -27.4 (c = 0.030 in
isopropanol); TOF–MS (ESI+); m/z calcd. for C15H13FN2S (M+1) 289.05, Found 289.00; Anal.
Calcd. For C15H13FN2S: C, 66.15; H, 4.81; N, 10.29, S, 11.77. Found: C, 66.11; H, 4.80; N,
10.25, S, 11.75; HPLC (CHIRALPAK OD, i-PrOH/ Hexane = 10/90, Flow rate 0.8 mL/ min, λ
= 247 nm): t (major) = 12.56 min, t (minor) = 11.65 min, er = 81.5:18.5.
2-(6,7-dihydrothieno[3,2-c]pyridin-5(4H)-yl)-2-(naphthalen-1-yl) acetonitrile (4i).
o
1
84 mg, 93% yield, white solid (amorphous); mp 68-70 C; H NMR (500 MHz, CDCl3): δ 8.14
(t, J = 5.0 Hz, 1H), 7.92-7.87 (m, 3H), 7.54-7.50 (m, 3H), 7.07 (d, J = 5.0 Hz, 1H), 6.69 (d, J =
5.0 Hz, 1H), 5.67 (s, 1H), 3.85 (d, J = 14.0 Hz, 1H), 3.65 (d, J = 14.0 Hz, 1H), 3.00 ( t, J = 5.5
13
Hz, 2H), 2.94-2.89 (m, 1H), 2.80-2.74 (m, 1H); C NMR (125 MHz, CDCl3); δ 135.5, 134.4,
134.1, 132.4, 131.7, 130.1, 129.7, 128.3, 127.7, 126.5, 126.2, 125.2, 124.5, 116.9, 62.1, 57.2,
48.9, 27.1; [α]D32 = -32.4 (c = 0.035 in isopropanol); TOF–MS (ESI+); m/z calcd. for C19H16N2S
ACS Paragon Plus Environment