T. Nakagawa et al.
Bull. Chem. Soc. Jpn., 77, No. 8 (2004) 1565
13C NMR (68 MHz, CDCl3) ꢂ 19.0, 22.8, 47.6, 52.1, 77.9, 127.9,
129.0, 133.5, 138.4, 178.0.
Methyl 3-Hydroxy-2,2-dimethyl-3-(4-nitrophenyl)propio-
for C13H22NaO4Siþ [M + Na]þ 293.1181, found m=z 293.1191.
S-Ethyl 3-Hydroxy-3-phenylpropanethioate (18).4c,16 Color-
1
less oil; IR (neat, cmꢁ1) 3502, 3425, 2970, 2924, 1682; H NMR
nate (10).4c
White crystals; mp 114.5 ꢂC; IR (neat, cmꢁ1
)
(270 MHz, CDCl3) ꢂ 1.25 (t, J ¼ 7:0 Hz, 3H), 2.84–3.04 (m,
4H), 3.11–3.17 (brs, 1H), 5.12–5.21 (m, 1H), 7.23–7.40 (m, 1H);
13C NMR (68 MHz, CDCl3) ꢂ 14.6, 23.5, 52.5, 70.8, 125.5,
127.7, 128.4, 142.2, 198.7.
S-t-Butyl 3-Hydroxy-3-phenylpropanethioate (19).16 Color-
less oil; IR (neat, cmꢁ1) 3487, 3356, 2962, 2916, 1674, 1041;
1H NMR (270 MHz, CDCl3) ꢂ 1.48 (s, 9H), 2.78–2.95 (m, 2H),
3.20 (brs, 1H), 5.15 (dd, J ¼ 4:1, 8.6 Hz, 1H) 7.24–7.36 (m,
5H); 13C NMR (68 MHz, CDCl3) ꢂ 22.6, 48.5, 52.6, 70.7, 125.4,
127.5, 128.2, 142.0, 199.6.
S-Ethyl 3-Hydroxy-2-methyl-3-phenylpropanethioate (20).16
syn Isomer: Colorless oil; IR (neat, cmꢁ1) 3494, 3363, 2970, 2924,
1674, 964; 1H NMR (270 MHz, CDCl3) ꢂ 1.16 (d, J ¼ 7:0 Hz, 3H),
1.22 (t, J ¼ 7:6 Hz, 3H), 2.87 (q, J ¼ 7:6 Hz, 2H), 2.90 (dq,
J ¼ 4:1, 7.0 Hz, 2H), 2.90 (brs, 1H), 5.10 (d, J ¼ 4:1 Hz, 1H)
7.24–7.34 (m, 5H); 13C NMR (68 MHz, CDCl3) ꢂ 11.4, 14.6,
23.3, 54.9, 73.7, 125.9, 127.4, 128.1, 141.0, 203.9. anti Isomer:
Colorless oil; IR (neat, cmꢁ1) 3464, 3332, 2962, 2931, 1674,
964; 1H NMR (270 MHz, CDCl3) ꢂ 1.02 (d, J ¼ 7:3 Hz, 3H),
1.26 (t, J ¼ 7:6 Hz, 3H), 2.69 (brs, 1H), 2.92 (q, J ¼ 7:6 Hz,
2H), 3.00 (dq, J ¼ 7:0, 8.4 Hz, 2H), 4.81 (d, J ¼ 8:4 Hz, 1H)
7.28–7.40 (m, 5H); 13C NMR (68 MHz, CDCl3) ꢂ 14.6, 15.5,
23.3, 55.4, 76.6, 126.6, 128.1, 128.5, 141.6, 203.7.
1
3517, 2985, 1712, 1519; H NMR (270 MHz, CDCl3) ꢂ 1.13 (s,
3 H), 1.15 (s, 3H), 3.74 (s, 3H), 5.01 (s, 1H), 7.41–7.62 (m, 2H),
8.09–8.32 (m, 2H); 13C NMR (68 MHz, CDCl3) ꢂ 19.2, 22.7,
47.6, 52.3, 77.7, 122.9, 128.6, 147.3, 147.6, 177.7.
Methyl 3-Hydroxy-2,2-dimethyl-5-phenylpentanoate (11).4c
Colorless oil; IR (neat, cmꢁ1) 3465, 2939, 1720; 1H NMR (270
MHz, CDCl3) ꢂ 1.16 (s, 3H), 1.18 (s, 3H), 1.53–1.81 (m, 2H),
2.51 (s, 1H), 2.59–2.70 (m, 1H), 2.90–3.00 (m, 1H), 3.60–3.67
(m, 1H), 3.68 (s, 3H), 7.15–7.31 (m, 5H); 13C NMR (68 MHz,
CDCl3) ꢂ 20.3, 22.4, 32.8, 33.6, 47.1, 51.9, 76.0, 125.8, 128.4,
128.5, 142.1, 178.2.
Methyl 3-Ethoxycarbonyl-2,2-dimethyl-3-phenyl-3-trimeth-
ylsiloxypropionate (12). Colorless oil; IR (neat, cmꢁ1) 2939,
1736, 1250, 1142; 1H NMR (270 MHz, CDCl3) ꢂ 0.09 (s, 9H),
1.21 (s, 3H), 1.27 (s, 3H), 1.37 (t, J ¼ 7:0 Hz, 3H), 3.62 (s, 3H),
4.22–4.41 (m, 2H), 7.23–7.25 (m, 3H), 7.53–7.56 (m, 2H);
13C NMR (68 MHz, CDCl3) ꢂ 2.3, 14.2, 21.8, 23.0, 51.6, 52.7,
61.6, 81.2, 127.1, 127.4, 127.6, 138.8, 172.3, 175.9; HRMS
(FAB+) calcd for C18H28LiO5Siþ [M + Li]þ 359.1861, found
m=z 359.1867.
Methyl 3-(4-Dimethylaminophenyl)-2,2-dimethyl-3-trimeth-
ylsiloxypropionate (13).4c White powder; mp 80.1 ꢂC; IR (neat,
cmꢁ1) 2978, 1728, 1612, 1519, 1458, 1349, 1250, 1073; 1H NMR
(270 MHz, CDCl3) ꢂ ꢁ0:07 (s, 9H), 1.00 (s, 3H), 1.09 (s, 3H), 2.91
(s, 6H), 3.65 (s, 3H), 4.87 (s, 1H), 6.59 (d, J ¼ 8:7 Hz, 2H), 7.31 (d,
J ¼ 8:7 Hz, 2H); 13C NMR (68 MHz, CDCl3) ꢂ ꢁ0:1, 18.8, 21.9,
40.5, 49.2, 51.5, 79.0, 111.3, 128.4, 128.5, 149.8, 177.6.
Methyl 2,2-Dimethyl-3-(2-pyridyl)-3-trimethylsiloxypropio-
nate (14).4c Colorless oil; IR (neat, cmꢁ1) 3626, 3186, 2993,
1728; 1H NMR (270 MHz, CDCl3) ꢂ ꢁ0:04 (s, 9H), 0.98 (s,
3H), 1.12 (s, 3H), 3.65 (s, 3H), 5.06 (s, 1H), 7.07–7.17 (m, 1H),
7.34–7.44 (m, 1H), 7.56–7.70 (m, 1H), 8.40–8.49 (m, 1H);
13C NMR (68 MHz, CDCl3) ꢂ 0.0, 20.2, 21.0, 48.7, 51.7, 79.8,
122.1, 135.6, 147.8, 161.1, 176.6.
S-t-Butyl
3-Hydroxy-2-methyl-3-phenylpropanethioate
(21).17 syn Isomer: Colorless oil; IR (neat, cmꢁ1) 3340, 2924,
1
1666, 1458, 957; H NMR (270 MHz, CDCl3) ꢂ 1.13 (d, J ¼ 7:0
Hz, 3H), 1.43 (s, 9H), 2.76–2.85 (m, 1H), 2.99 (brs, 1H), 5.07
(d, J ¼ 3:8 Hz, 1H) 7.24–7.34 (m, 5H); 13C NMR (68 MHz,
CDCl3) ꢂ 11.5, 29.7, 48.3, 55.0, 73.8, 126.0, 127.3, 128.1, 141.1,
204.9. anti Isomer: Colorless oil; IR (neat, cmꢁ1) 3379, 2962,
2916, 1674, 1458, 957; 1H NMR (270 MHz, CDCl3) ꢂ 1.01 (d, J ¼
7:0 Hz, 3H), 1.46 (s, 9H), 2.79 (d, J ¼ 4:3 Hz, 1H), 2.88 (dq,
J ¼ 0:8, 7.0 Hz, 1H), 4.77 (dd, J ¼ 3:0, 7.8 Hz, 1H) 7.27–7.38
(m, 5H); 13C NMR (68 MHz, CDCl3) ꢂ 15.6, 29.8, 48.4, 55.6,
76.6, 126.5, 127.9, 128.3, 141.6, 204.3.
Methyl 2,2-Dimethyl-3-(1-methyl-2-pyrrolyl)-3-trimethylsil-
oxypropionate (15). Colorless oil; IR (neat, cmꢁ1) 2947, 1736,
1257, 1072, 879, 849; H NMR (270 MHz, C6D6) ꢂ 0.05 (s, 9H),
1.09 (s, 3H), 1.50 (s, 3H), 3.10 (s, 3H), 3.53 (s, 3H), 5.24 (s,
1H), 6.25 (dd, J ¼ 2:4, 3.5 Hz, 1H), 6.29–6.31 (m, 2H); 13C NMR
(68 MHz, C6D6) ꢂ 0.1, 19.5, 22.5, 34.6, 50.0, 51.5, 73.4, 107.6,
109.9, 122.5, 131.3, 176.8; HRMS (FAB+) calcd for
C14H25NO3Siþ [M]þ 283.1604, found m=z 283.1621.
S-t-Butyl 3-Hydroxy-2,2-dimethyl-3-phenylpropanethioate
(22).18
White crystals; mp 69.0 ꢂC; IR (neat, cmꢁ1) 3587,
3471, 2924, 1651, 941; 1H NMR (270 MHz, CDCl3) ꢂ 1.11 (s,
3H), 1.47 (s, 9H), 3.14 (d, J ¼ 4:1 Hz, 1H), 4.89 (d, J ¼ 3:5 Hz,
1H) 7.29–7.32 (m, 5H); 13C NMR (68 MHz, CDCl3) ꢂ 19.4,
23.7, 29.7, 47.8, 54.8, 79.0, 127.6, 127.7, 139.9, 208.5; Anal. Calcd
for C15H22O2S: C, 67.63; H, 8.32%. Found: C, 67.24; H, 8.17%.
3-Hydroxy-1,3-diphenyl-1-propanone (23).4c,13c–e Colorless
oil; IR (neat, cmꢁ1) 3548, 3425, 1673; 1H NMR (270 MHz, CDCl3)
ꢂ 3.37 (d, J ¼ 6:0 Hz, 2H), 5.34 (t, J ¼ 6:0 Hz, 1H), 7.29–7.58 (m,
8H), 7.81–8.12 (m, 2H); 13C NMR (68 MHz, CDCl3) ꢂ 47.4, 70.0,
125.7, 127.7, 128.1, 128.6, 128.7, 133.6, 136.5, 142.9, 200.2.
1
Methyl 3-(1-t-Butoxycarbonyl-3-indolyl)-2,2-dimethyl-3-tri-
methylsiloxypropionate (16).4c Colorless oil; IR (neat, cmꢁ1
)
2978, 1736, 1458, 1373, 1257, 1149, 1280, 856, 756; 1H NMR
(270 MHz, CDCl3) ꢂ ꢁ0:04 (s, 9H), 1.09 (s, 3H), 1.25 (s, 3H),
1.68 (s, 9H), 3.67 (s, 3H), 5.26 (s, 1H), 7.12–7.37 (m, 2H), 7.43
(s, 1H), 7.68–7.84 (m, 1H), 7.99–8.22 (m, 1H); 13C NMR (68
MHz, CDCl3) ꢂ ꢁ0:2, 19.9, 21.9, 28.2, 49.7, 51.7, 74.1, 83.7,
114.9, 120.8, 121.5, 122.3, 124.0, 129.9, 135.2, 149.7, 168.1,
177.2.
3-Hydroxy-2-methyl-1,3-diphenyl-1-propanone
(24).13c–e
(syn/anti = 63/37) Colorless oil; IR (neat, cmꢁ1) 3510, 3417,
1
3047, 1674; H NMR (270 MHz, CDCl3) ꢂ 1.05 (d, J ¼ 7:0 Hz,
1.11H), 1.19 (d, J ¼ 7:3 Hz, 1.89H), 3.07 (brs, 0.37H), 3.65 (brs,
0.63H), 3.69 (dq, J ¼ 3:2, 7.3 Hz, 1.26H), 3.83 (dq, J ¼ 7:7, 7.7
Hz, 0.74H), 4.98 (d, J ¼ 8:1 Hz, 0.37H), 5.23 (d, J ¼ 3:2 Hz,
0.63H), 7.22–7.60 (m, 8H), 7.90–7.98 (m, 2H); 13C NMR (68
MHz, CDCl3) syn isomer: ꢂ 11.3, 47.0, 73.0, 125.9, 127.1,
128.1, 128.3, 128.6, 133.4, 135.4, 141.6, 205.5; anti Isomer: ꢂ
15.8, 47.8, 76.7, 126.6, 127.8, 128.3, 128.5, 133.2, 136.5, 142.0,
204.6.
Methyl 3-(2-Furyl)-2,2-dimethyl-3-trimethylsiloxypropio-
nate (17).15 Colorless oil; IR (neat, cmꢁ1) 2962, 1736, 1257,
1142, 1088, 864; 1H NMR (270 MHz, CDCl3) ꢂ ꢁ0:02 (s, 9H),
1.02 (s, 3H), 1.21 (s, 3H), 3.66 (s, 3H), 4.99 (s, 1H), 6.18 (d, J ¼
2:7 Hz, 1H), 6.29 (dd, J ¼ 1:9, 3.2 Hz, 1H), 7.32 (t, J ¼ 0:8 Hz,
1H); 13C NMR (68 MHz, CDCl3) ꢂ ꢁ0:3, 19.6, 21.3, 48.6, 51.8,
73.4, 107.8, 109.8, 141.4, 154.2, 176.6; HRMS (FAB+) calcd
Methyl 3-Hydroxy-2-methyl-3-phenylpropionate (25).4c,13b