Page 25 of 31
The Journal of Organic Chemistry
1
white solid (25 mg, 22%). TLC (33% ethyl acetate in hexanes): Rf = 0.73 (UV, CAM). H NMR (400 MHz, CD2Cl2) δ 7.52 ‒ 7.25 (m,
5H), 6.41 (s, 1H), 2.44 ‒ 2.11 (m, 4H), 1.74 (s, 3H). 13C NMR (100 MHz, CD2Cl2) δ 196.7, 164.6, 143.2, 130.8, 129.2, 127.7, 126.9, 47.6,
39.9, 34.6, 26.5. IR (DiamondꢀATR, neat) ṽmax: 3060 (w), 2973 (w), 1734 (w), 1682 (vs), 1596 (m), 1496 (m), 1445 (m), 1298 (m), 1207
(m), 1071 (w), 970 (m) cmꢀ1. HRꢀMS (EI): calcd for (C13H13O35Cl)+: 220.0655, found: 220.0651.
1
2
3
4
5
6
7
8
9
3ꢀChloroꢀ4,4ꢀdiphenylcyclohexꢀ2ꢀenꢀ1ꢀone (33b). The general procedure was followed, using 4,4ꢀdiphenylcyclohexꢀ2ꢀenꢀ1ꢀone (124 mg,
0.50 mmol), affording 33b after purification by flash column chromatography on silica gel (11% ethyl acetate in hexane) as a white solid
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
1
(25 mg, 18%). TLC (33% ethyl acetate in hexanes): Rf = 0.83 (UV, CAM). H NMR (400 MHz, CD2Cl2) δ 7.42‒7.28 (m, 10H), 6.51 (s,
1H), 2.86 (t, J = 6.3 Hz, 2H), 2.23 (t, J = 6.5 Hz, 2H). 13C NMR (100 MHz, CD2Cl2) δ 196.4, 163.4, 142.5, 131.7, 129.5, 128.8, 128.0,
57.6, 39.3, 35.0. IR (DiamondꢀATR, neat) ṽmax: 3059 (w), 2958 (w), 1681 (s), 1594 (m), 1496 (m), 1448 (m), 1290 (m), 1210 (w), 1171
(w), 980 (m), 949 (w) cmꢀ1. HRꢀMS (EI): calcd for (C18H15O35Cl)+: 282.0811, found: 282.0819.
Methyl 2ꢀchloroꢀ1ꢀmethylꢀ4ꢀoxoꢀ2ꢀcyclohexeneꢀ1ꢀcarboxylate (34b). The general procedure was followed, using methyl 1ꢀmethylꢀ4ꢀ
oxoꢀ2ꢀcyclohexeneꢀ1ꢀcarboxylate (134 mg, 0.50 mmol), affording 34b after purification by flash column chromatography on silica gel (9%
ethyl acetate in hexane) as a colorless oil (35 mg, 34%). TLC (33% ethyl acetate in hexanes): Rf = 0.68 (UV, CAM). 1H NMR (400 MHz,
CDCl3) δ 6.28 (s, 1H), 3.78 (s, 3H), 2.58–2.40 (m, 3H), 2.12‒1.99 (m, 1H), 1.58 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 195.7, 172.7,
159.3, 129.8, 53.2, 50.2, 34.2, 34.1, 22.9. IR (DiamondꢀATR, neat) ṽmax: 2956 (w), 1735 (s), 1684 (s), 1604 (m), 1454 (m), 1302 (m), 1255
(m) 1196 (m), 1177 (m), 1117 (m), 977 (m) cmꢀ1. HRꢀMS (EI): calcd for (C9H11O335Cl)+: 202.0397, found: 202.0388.
(2ꢀChloroꢀ1ꢀmethylꢀ4ꢀoxocyclohexꢀ2ꢀenꢀ1ꢀyl)methyl pivalate (35b). The general procedure was followed, using (1ꢀmethylꢀ4ꢀ
oxocyclohexꢀ2ꢀenꢀ1ꢀyl)methyl pivalate (66) (112 mg, 0.50 mmol), affording 35b after purification by flash column chromatography on
silica gel (9% ethyl acetate in hexane) as a yellow oil (32 mg, 24%). TLC (33% ethyl acetate in hexanes): Rf = 0.69 (UV, CAM). 1H NMR
(400 MHz, CDCl3) δ 6.25 (s, 1H), 4.32 (d, J = 11.1 Hz, 1H), 3.93 (d, J = 11.2 Hz, 1H), 2.56‒2.49 (m, 2H), 2.26 (ddd, J = 13.7, 9.5, 6.2 Hz,
1H), 1.91 (ddd, J = 13.7, 6.7, 5.9 Hz, 1H), 1.30 (s, 3H), 1.18 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 196.3, 178.1, 162.9, 130.0, 68.8, 42.2,
39.0, 33.8, 32.0, 27.2, 21.2. IR (DiamondꢀATR, neat) ṽmax: 2973 (w), 2936 (w), 1730 (s), 1678 (s), 1601 (m), 1480 (m), 1461 (m), 1280 (s),
1141 (s) cmꢀ1. HRꢀMS (EI): calcd for (C13H20O335Cl)+ (M+H)+: 259.1101, found: 259.1110.
4ꢀ((Benzyloxy)methyl)ꢀ3ꢀchlorocyclohexꢀ2ꢀenꢀ1ꢀone (37b). The general procedure was followed, using 4ꢀ[(phenylmethoxy)methyl]ꢀ2ꢀ
cyclohexꢀ2ꢀenꢀ1ꢀone (108 mg, 0.50 mmol), affording 37b after purification by flash column chromatography on silica gel (9% ethyl aceꢀ
1
tate in hexane) as a yellow oil (25 mg, 20%). TLC (33% ethyl acetate in hexanes): Rf = 0.67 (UV, CAM). H NMR (400 MHz, CDCl3) δ
7.39–7.27 (m, 5H), 6.27 (s, 1H), 4.61–4.51 (m, 2H), 3.75 (d, J = 5.1 Hz, 2H), 2.89‒2.82 (m, 1H), 2.56 (ddd, J = 16.6, 9.8, 5.8 Hz, 1H),
2.36 (app dt, J = 17.0, 5.8 Hz, 1H), 2.29‒2.15 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 196.9, 158.7, 137.7, 130.0, 128.5, 127.9, 127.6,
73.4, 69.6, 42.9, 34.2, 25.2. IR (DiamondꢀATR, neat) ṽmax: 3031 (w), 2924 (w), 2864 (w), 1725 (w), 1678 (vs), 1604 (m), 1453 (m), 1294
(m), 1282 (m), 1235 (m), 1200 (m), 1100 (s), 979 (m) cmꢀ1. HRꢀMS (EI): calcd for (C14H15O236Cl)+: 250.0761, found: 250.0763.
3ꢀChloroꢀ4ꢀ(propꢀ2ꢀynꢀ1ꢀyl)cyclohexꢀ2ꢀenꢀ1ꢀone (39b). The general procedure was followed, using 4ꢀ(propꢀ2ꢀynꢀ1ꢀyl)cyclohexꢀ2ꢀenꢀ1ꢀ
one (67.1 mg, 0.50 mmol), affording 39b after purification by flash column chromatography on silica gel (33% ethyl acetate in hexane) as
1
a colorless oil (26 mg, 30%). TLC (33% ethyl acetate in hexanes): Rf = 0.78 (UV, CAM). H NMR (400 MHz, CDCl3) δ 6.25 (s, 1H),
2.86‒2.78 (m, 1H), 2.72 (dt, J = 16.9, 3.2 Hz, 1H), 2.63‒2.52 (m, 2H), 2.39 (ddd, J = 17.1, 8.2, 5.0 Hz, 1H), 2.26 (dddd, J = 19.3, 16.1,
ACS Paragon Plus Environment