10.1002/ejoc.201601598
European Journal of Organic Chemistry
FULL PAPER
J = 3.0, 5.3, 13.7 Hz, 1H, 6’-Hb), 2.41 (ddd, J = 3.0, 5.2, 14.3 Hz, 1H, 2’-
Hb), 3.66 (s, 3H, OCH3), 4.07-4.11 (m, 1H, 4-H), 4.35 (s, 1H, OH), 5.73
(br s, 1H, C=CH), 7.17-7.23 (m, 2H, Ph), 7.26-7.29 (m, 3H, Ph) ppm.13C-
NMR (125 MHz, CDCl3) δ = 12.0 (6-C), 26.9 (3’-C), 27.8 (C(CH3)3), 28.1
(5’-C), 28.6 (5-C), 29.7 (2’-C), 32.3 (C(CH3)3), 37.5 (6’-C), 47.9 (1’-C),
53.4 (OCH3), 54.9 (4-C), 83.6 (2-C), 115.6 (C=CH), 127.6 (4-C-Ph),
128.5 (2-C-Ph), 128.8 (3-C-Ph), 138.7 (1-C-Ph), 149.4 (1’-C), 171.2 (1-C),
206.0 (3-C) ppm.
TLC: Rf= 0.36 (n-pentane/EtOAc 10:1). 1H-NMR
(500 MHz, CDCl3) δ = 0.26 (ddd, J = 3.7, 12.8, 25.7 Hz, 1H, Cy), 0.64 (s,
9H, C(CH3)3), 0.81-0.92 (m, 2H, Cy), 0.98-1.12 (m, 1H, Cy), 1.36-1.85 (m,
3H, Cy), 2.24-2.43 (m, 2H, Cy), 3.73 (s, 3H, OCH3), 5.00 (s, 1H, OH),
6.16 (s, 1H, C=CH), 7.39-7.47 (m, 2H, Ph), 7.56 (t, J = 7.42 Hz, 1H, Ph),
8.06-8.12 (m, 2H, Ph) ppm. Signals of major diastereomer are reported
only. 13C-NMR (125 MHz, CDCl3) δ =27.0 (Cy), 27.5 (C(CH3)3), 27.9 (Cy),
28.9 (Cy), 29.9 (Cy), 32.3 (C(CH3)3), 47.5 (4'-C), 53.5 (OCH3), 80.8 (2-C),
118.3 (C=CH), 128.4 (Ph), 130.8 (Ph), 132.2 (Ph), 134.1 (Ph), 149.5
(C=CH), 171.5 (1-C), 196.8 (3-C) ppm. Signals of major diastereomer are
reported only. HRMS: ESI+ calcd. for C21H28O4Na [M+Na]+: 367.1880,
found: 367.1881. IR (ATR): ν =3462 (br, w), 3062 (w), 2947 (m), 2864 (w),
1742 (m), 1681 (s), 1598 (w), 1581 (w), 1448 (m), 1392 (w), 1365 (m),
1260 (w), 1223 (s), 1167 (m), 1130 (m), 1087 (w), 1068 (w), 1031 (w),
1012 (w), 988 (w), 940 (w), 911 (w), 833 (w), 806 (w), 749 (w), 690 (m),
631 (w), 549 (w) cm-1.
Methyl 2-((4-tert-butyl)cyclohexylidene)methyl)-2-hydroxy-3-oxo-6-
phenylhexanoate (38c)
The title compound was prepared from alkenyl iodide29 (0.3 M in THF,
1.00 mL, 0.30 mmol, 1.0 equiv.), sec-butyl lithium (1.4 M in cyclohexane,
0.43 mL, 0.60 mmol, 2.0 equiv.), dineopentylzinc (1.0 M in benzene,
0.60 mL, 0.60 mmol, 2.0 equiv.) and α,β-diketoester 14c (0.5 M in CH2Cl2,
1.20 mL, 0.60 mmol, 2.0 equiv.) according to GP8 to afford 38c (50 mg,
181 µmol, 60%, d.r. 1.2:1) as colourless oil after SCC (n-pentane/ EtOAc
15:1).
Methyl 2-((4-(tert-butyl)cyclohexylidene)methyl)-2-hydroxy-3-oxo-4-
phenylhexanoate (38b)
Mixture of diastereomers:HRMS: ESI+ calcd. for
C24H34O4Na [M+Na]+: 409.2349, found: 409.2352. IR (ATR): ν = 3472 (w),
3026 (w), 2945 (m), 2865 (w), 2841 (w), 1717 (s), 1660 (w), 1496 (w),
1451 (w), 1437 (w), 1394 (w), 1364 (m), 1253 (w), 1237 (s), 1172 (w),
1142 (w), 1098 (w), 1030 (w), 1011 (w), 990 (w), 925 (w), 830 (w), 744
(m), 700 (s), 652 (w), 491 (w) cm-1.
The title compound was prepared from alkenyl iodide29 (0.3 M in THF,
1.00 mL, 0.30 mmol, 1.0 equiv.), sec-butyl lithium (1.4 M in cyclohexane,
0.43 mL, 0.60 mmol, 2.0 equiv.), dineopentylzinc (1.0 M in benzene,
0.60 mL, 0.60 mmol, 2.0 equiv.) and α,β-diketoester 14a (0.5 M in CH2Cl2,
1.20 mL, 0.60 mmol, 2.0 equiv.) according to GP8 to afford 38b (fist
diastereomer 25 mg, 65 µmol, 22%) as colourless foam and 38b (second
diastereomer 27 mg, 70 µmol, 23%) as colourless solid after SCC
(n-pentane/ EtOAc 25:1).
1. diastereomer
TLC: Rf= 0.26 (n-pentane/EtOAc 10:1). 1H-NMR (500 MHz, CDCl3) δ =
0.83 (s, 9H, C(CH3)3), 0.97-1.08 (m, 1H, 3'-Ha), 1.08-1.17 (m, 2H, 5'-Ha,
4'-H), 1.53 (td, J = 4.3, 13.1 Hz, 1H, 6'-Ha), 1.77-1.83 (m, 1H, 3'-Hb),
1.83-1.88 (m, 1H, 5'-Hb), 1.91 (dt, J = 7.3, 14.7 Hz, 2H, 5-H), 1.98-2.06
(m, 1H, 2'-Ha), 2.26-2.32 (m, 1H, 2'-Hb), 2.56-2.61 (m, 3H, 6'-Hb, 6-H),
2.64 (t, J = 7.2 Hz, 2H, 4-H), 3.76 (s, 3H, OCH3), 4.43 (s, 1H, OH), 5.74
(s, 1H, C=CH), 7.13-7.21 (m, 3H, Ph), 7.26-7.30 (m, 2H, Ph) ppm. 13C-
NMR (125 MHz, CDCl3) δ = 25.6 (5-C), 27.7 (C(CH3)3), 28.2 (2'-C), 29.2
(3'-C), 29.9 (6'-C), 32.6 (C(CH3)3), 35.0 (6-C), 36.5 (4-C), 37.6 (5'-C),
48.0 (4'-C), 53.5 (OCH3), 82.9 (2-C), 116.6 (C=CH), 126.2 (4-C-Ph),
128.5 (3-C-Ph), 128.5 (2-C-Ph), 141.5 (1-C-Ph), 150.0 (1’-C), 171.4 (1-C),
206.4 (3-C) ppm.
Mixture of diastereomers: HRMS: ESI+ calcd. for
C24H34O4Na [M+Na]+: 409.2349, found: 409.2352. IR (ATR): ν = 3477 (br,
w), 3062 (w), 3030 (w), 2948 (s), 2869 (w), 2840 (w), 1744 (w), 1716 (s),
1659 (w), 1600 (w), 1453 (m), 1438 (w), 1365 (w), 1252 (w), 1237 (s),
1174 (w), 1145 (w), 1121 (w), 1073 (w), 1032 (w), 992 (w), 925 (w), 899
(w), 855 (w), 831 (w), 752 (w), 700 (m), 574 (w), 502 (w) cm-1.
1. diastereomer:
TLC: Rf= 0.44 (n-pentane/EtOAc 10:1). 1H-NMR (500 MHz, CDCl3) δ =
0.50 (m, 1H, 2’-Ha), 0.71-0.75 (m, 12H, 6-H, C(CH3)3), 0.80-0.87 (m, 2H,
4’-H, 3’-Ha), 0.94-1.04 (ddd, J = 3.8, 12.8, 25.3 Hz, 1H, 5’-Ha), 1.53-1.64
(m, 2H, 3’-Hb, 5’-Hb), 1.70-1.80 (m, 2H, 6’-Ha, 5-Ha), 1.90-1.98 (m, 1H, 5-
Hb), 2.10-2.20 (m, 2H, 2’-Hb, 6’-Hb), 3.70 (s, 3H, OCH3), 4.03 (t, J = 7.5
Hz, 1H, 4-H), 4.39 (s, 1H, OH), 5.78 (br s, 1H, C=CH), 7.11-7.45 (m, 5H,
Ph) ppm.13C-NMR (125 MHz, CDCl3) δ = 12.0 (6-C), 27.7 (C(CH3)3), 27.9
(3’-C), 28.3 (5-C), 28.9 (5’-C), 29.3 (2’-C), 32.5 (C(CH3)3), 37.2 (6’-C),
47.8 (4’-C), 53.4 (OCH3), 55.4 (4-C), 83.4 (2-C), 115.3 (C=CH), 127.2 (4-
C-Ph), 128.4 (2-C-Ph), 128.6 (3-C-Ph), 138.9 (1-C-Ph), 151.4 (1’-C),
171.1 (1-C), 206.6 (3-C) ppm.
2. diastereomer
TLC: Rf= 0.21 (n-pentane/EtOAc 10:1). 1H-NMR (500 MHz, CDCl3) δ =
0.91 (s, 9H, C(CH3)3), 0.94-1.00 (m, 1H, 3’-Ha), 1.09-1.19 (m, 1H, 5’-Ha),
1.19-1.28 (m, 1H, 4’-H),1.80-1.91 (m, 2H, 3’-Hb, 6’-Ha), 1.94-2.07 (m, 3H,
5’-Hb), 2.12-2.19 (m, 1H, 2’-Ha), 2.37-2.43 (m, 1H, 2’-Hb), 2.65-2.86 (m,
5H, 6’-Hb, 6-H, 4-H), 3.86 (s, 3H, OCH3), 4.51 (s, 1H, OH), 5.81 (s, 1H,
C=CH), 7.24-7.31 (m, 3H, Ph), 7.35-7.39 (m, 2H, Ph) ppm. 13C-NMR
(125 MHz, CDCl3) δ = 25.8 (5-C), 27.6 (C(CH3)3), 27.9 (2'-C), 29.1 (3'-C),
29.7 (6'-C), 32.5 (C(CH3)3), 35.1 (6-C), 36.5 (4-C), 37.6 (5'-C), 47.8 (4'-C),
53.5 (OCH3), 83.0 (2-C), 116.7 (C=CH), 126.2 (4-C-Ph), 128.5 (3-C-Ph),
128.5 (2-C-Ph), 141.4 (1-C-Ph), 149.7 (1’-C), 171.4 (1-C), 206.3 (3-C)
ppm.
Methyl 2-((4-(tert-butyl)cylohexylidene)methyl)-2-hydroxy-3-(4-
methoxyphenyl)-3-oxopropanoate (38e)
The title compound was prepared from alkenyl iodide29 (0.3 M in THF,
1.00 mL, 0.30 mmol, 1.0 equiv.), sec-butyl lithium (1.4 M in cyclohexane,
0.43 mL, 0.60 mmol, 2.0 equiv.), dineopentylzinc (1.0 M in benzene,
0.60 mL, 0.60 mmol, 2.0 equiv.) and α,β-diketoester 14e (0.5 M in CH2Cl2,
1.20 mL, 0.60 mmol, 2.0 equiv.) according to GP8 to afford 38e (69 mg,
184 µmol, 61%, d.r. 1.2:1) as colourless oil after SCC (n-pentane/ EtOAc
20:1 → n-pentane/ EtOAc 15:1).
2. diastereomer:
TLC: Rf= 0.42 (n-pentane/EtOAc 10:1). M.p.: 99.5 °C. 1H-NMR (500 MHz,
CDCl3) δ = 0.13 (ddd, J = 3.8, 12.8, 25.7 Hz, 1H, 3’-Ha), 0.65 (ddd, J =
3.9, 12.5, 25.5 Hz, 1H, 5’-Ha), 0.71 (s, 9H, C(CH3)3), 0.75 (m, 3H, 6-H),
0.89-0.94 (m, 1H, 4’-H), 1.43-1.49 (m, 1H, 3’-Hb), 1.60-1.66 (m, 2H, 5’-Hb,
2’-Ha), 1.71-1.78 (m, 1H, 5-Ha), 1.87-1.95 (m, 2H, 5-Hb, 6’-Ha), 2.17 (ddd,
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