P. Thirupathi, S.S. Kim / Tetrahedron 66 (2010) 2995–3003
3001
Compound 5a. White solid, 1H NMR (400 MHz, CDCl3)
d
; 7.27–
132.9, 129.1, 129.0, 128.9, 128.8, 64.8, 61.7, 49.2, 30.1, 13.8; HRMS–
7.24 (m, 8H), 7.18–7.13 (m, 2H), 4.81 (d, J¼12.0 Hz, 1H), 4.81 (d,
FAB (m/z): [M]þ calcd for C19H19Cl2O3: 365.0711, found: 365.0711.
J¼12.0 Hz, 1H), 4.73 (d, J¼12.5 Hz, 1H), 2.0 (s, 3H); 13C NMR
Compound 5m. Viscous, 1H NMR (400 MHz, CDCl3)
d; 7.27–7.21
(100 MHz, CDCl3)
d
: 202.9, 141.2, 128.8, 127.6, 126.9, 74.4, 51.1, 29.6.
(m, 4H), 6.95 (t, J¼8.8 Hz, 4H), 4.79 (d, J¼12.0 Hz, 1H), 4.46 (d,
Compound 5a. (Dimeric ether) White solid, 1H NMR (400 MHz,
J¼12.0 Hz, 1H), 4.00 (q, J¼7.0 Hz, 4H), 2.11 (s, 3H), 1.03 (t, J¼7.0 Hz,
CDCl3)
d
; 7.99 (d, J¼8.0 Hz, 4H), 7.56–754 (m, 2H), 7.51–7.49 (m,
4H); 13C NMR (100 MHz, CDCl3)
d: 201.1, 167.3, 162.8, 160.4, 137.1,
4H), 6.87 (s, 3H); 13C NMR (100 MHz, CDCl3)
129.3, 127.7, 93.7.
d
: 186.3, 136.1, 133.0,
136.9, 129.1, 129.0, 115.7, 115.4, 65.3, 61.6, 49.1, 29.9, 13.7; HRMS–
FAB (m/z): [M]þ calcd for C19H19F2O3: 333.1304, found: 333.1302.
Compound 5n. White solid, mp 101–102 ꢁC; 1H NMR (400 MHz,
Compound 5b. White solid, 1H NMR (400 MHz, CDCl3)
d
; 7.95 (d,
J¼8.4 Hz, 2H), 7.50–7.54 (m, 1H), 7.41 (d, J¼6.5 Hz, 2H), 7.37 (d,
J¼7.0 Hz, 2H), 7.32–7.28 (m, 2H), 7.26–7.20 (m, 3H), 7.15–7.11 (m,
2H), 7.05–7.02 (m, 1H), 5.02 (d, J¼12.0 Hz, 1H), 5.11 (d, J¼12.0 Hz,
CDCl3)
d
; 8.02 (d, J¼7.3 Hz, 2H), 7.54 (t, J¼7.3 Hz, 1H), 7.43 (t,
J¼7.3 Hz, 2H), 7.29 (d, J¼8.4 Hz, 2H), 7.14 (d, J¼8.8 Hz, 2H), 6.83 (d,
J¼8.8 Hz, 2H), 6.68 (d, J¼8.8 Hz, 2H), 5.34 (d, J¼11.7 Hz, 1H), 5.01 (d,
J¼11.7 Hz, 1H), 3.95–3.85 (m, 2H), 3.75 (s, 3H), 3.65 (s, 3H), 0.97 (t,
1H), 2.04 (s, 3H); 13C NMR (100 MHz, CDCl3)
d: 202.9, 194.2, 141.6,
141.2, 136.8, 133.6, 128.9, 128.7, 128.6, 128.0, 127.7, 127.0, 126.6, 68.8,
51.4, 27.8.
J¼7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d: 192.9, 167.7, 157.2,
157.9, 136.6, 134.1, 133.4, 129.0, 128.6, 128.5, 113.9, 113.8, 61.4, 59.8,
55.1, 55.0, 49.3, 13.7; HRMS–FAB (m/z): [M]þ calcd for C26H26O5:
418.1780, found: 418.1778.
Compound 5c. White solid, 1H NMR (400 MHz, CDCl3)
d; 7.83 (d,
J¼8.4 Hz, 4H), 7.58–7.44 (m, 3H), 7.53–7.44 (m, 3H), 7.35–7.30 (m,
4H), 7.25 (d, J¼8.4 Hz, 4H), 7.17–7.12 (m, 4H), 7.07–7.01 (m, 2H), 6.35
(d, J¼12.0 Hz, 1H), 5.36 (d, J¼12.0 Hz, 1H); 13C NMR (100 MHz,
Compound 7a. White solid, 1H NMR (400 MHz, CDCl3)
d; 7.89 (br
s, 1H), 7.32 (d, J¼8.4 Hz, 1H), 7.29–7.13 (m, 12H), 6.97 (t, J¼8.0 Hz,
CDCl3)
62.3, 52.4.
Compound 5d. White solid, 1H NMR (400 MHz, CDCl3)
d: 194.1, 141.7, 136.9, 133.2, 132.4, 128.6, 128.3, 127.2, 126.6,
1H), 6.54 (d, J¼2.0 Hz, 1H), 5.66 (s, 1H); 13C NMR (100 MHz, CDCl3)
d: 143.9, 136.7, 129.0, 128.2, 126.9, 126.2, 124.0, 122.1, 119.9, 119.4,
d; 7.23 (d,
111.0, 48.8.
Compound 7b. White solid, mp 117 ꢁC; 1H NMR (400 MHz,
CDCl3)
; 7.90 (br s,1H), 7.32 (d, J¼8.4 Hz, 2H), 7.23 (d, J¼8.4 Hz, 4H),
7.11–7.06 (m, 1H), 7.23 (d, J¼8.4 Hz, 4H), 6.91 (m, 1H), 6.56 (s, 1H),
5.67 (s, 1H), 3.84 (s, 6H); 13C NMR (100 MHz, CDCl3)
: 157.8, 136.6,
J¼8.5 Hz, 4H), 7.15 (d, J¼8.5 Hz, 4H), 4.80 (d, J¼12.5 Hz, 1H), 4.59 (d,
J¼12.0 Hz, 1H), 2.0 (s, 3H); 13C NMR (100 MHz, CDCl3)
139.3, 133.0, 129.1, 129.0, 74.3, 49.5, 29.6.
d
: 202.0,
d
Compound 5e. White solid, 1H NMR (400 MHz, CDCl3)
d
; 7.20 (d,
d
J¼8.6 Hz, 2H), 7.18 (d, J¼8.6 Hz, 2H), 6.95 (d, J¼8.6 Hz, 4H), 4.80 (d,
136.5, 129.7, 126.8, 123.8, 121.9, 120.3, 119.8, 119.1, 113.5, 111.0, 55.1,
47.0; HRMS–FAB (m/z): [M]þ calcd for C23H21NO2: 343.1572, found:
343.1572.
J¼12.5 Hz, 1H), 4.64 (d, J¼12.0 Hz, 1H), 1.99 (s, 3H); 13C NMR
(100 MHz, CDCl3) d: 203.0, 164.8, 159.8, 137.5, 129.9, 129.7, 116.7,
116.3, 75.4, 50.1, 30.2.
Compound 7c. White solid, mp 116–117 ꢁC; 1H NMR (400 MHz,
Compound 5f. White solid, 1H NMR (400 MHz, CDCl3)
d; 7.15 (d,
CDCl3)
d
; 7.43 (d, J¼7.8 Hz, 2H), 7.37 (d, J¼6.7 Hz, 1H), 7.34 (d,
J¼8.4 Hz, 4H), 6.78 (d, J¼8.6 Hz, 4H), 4.70 (d, J¼12.0 Hz,1H), 4.63 (d,
J¼8.0 Hz, 4H), 7.16 (t, J¼8.4 Hz, 1H), 7.00 (d, J¼8.4 Hz, 4H), 6.59 (s,
J¼12.0 Hz, 1H), 2.72 (s, 3H), 1.98 (s, 3H); 13C NMR (100 MHz, CDCl3)
1H), 5.78 (s, 1H), 3.89 (s, 6H), 3.76 (s, 3H); 13C NMR (100 MHz,
d
: 203.3, 158.3, 133.7, 128.6, 114.3, 74.9, 55.1, 49.7, 29.7.
CDCl3) d: 157.7, 137.3, 136.5, 129.6, 128.4, 127.2, 121.4, 119.9, 118.8,
Compound 5g. White solid, mp 107–108 ꢁC; 1H NMR (400 MHz,
118.6, 113.4, 108.9, 54.9, 47.0, 32.2; HRMS–FAB (m/z): [M]þ calcd for
C24H23NO2: 357.1729, found: 357.1729.
CDCl3)
d
; 7.95 (d, J¼8.4 Hz, 2H), 7.54–7.52 (m, 1H), 7.44–7.39 (m,
2H), 7.26 (d, J¼8.8 Hz, 2H), 7.13 (d, J¼8.8 Hz, 2H), 6.84 (d, J¼8.8 Hz,
2H), 6.67 (d, J¼8.8 Hz, 2H), 5.52 (d, J¼11.7 Hz, 1H), 5.02 (d,
J¼12.0 Hz, 1H), 3.75 (s, 3H), 3.65 (s, 3H), 2.04 (s, 3H); 13C NMR
Compound 7d. White solid, mp 129–130 ꢁC; 1H NMR (400 MHz,
CDCl3)
6.86 (d, J¼8.8 Hz, 5H), 6.70 (d, J¼2.0 Hz, 1H), 6.54 (d, J¼2.0 Hz, 1H),
5.56 (s, 1H), 3.80 (s, 6H), 3.72 (s, 3H); 13C NMR (100 MHz, CDCl3)
d
; 7.90 (br s, 1H), 7.20 (d, J¼9.0 Hz, 1H), 7.18 (d, J¼8.8 Hz, 4H),
(100 MHz, CDCl3)
d: 203.2, 194.4, 158.4, 158.0, 136.9, 134.2, 133.6,
d:
133.5, 129.0, 128.7, 128.5, 114.3, 113.9, 69.3, 55.1, 55.0, 49.9, 27.6.
157.8, 153.6, 136.4, 131.8, 129.7, 127.3, 124.6, 120.1, 113.5, 111.9, 111.6,
102.0, 55.7, 55.1, 47.1; HRMS–FAB (m/z): [M]þ calcd for C24H23NO3:
373.1678, found: 373.1678.
Compound 5h. White solid, 1H NMR (400 MHz, CDCl3)
d; 7.27–
7.25 (m, 8H), 7.18–7.14 (m, 2H), 4.77 (d, J¼12.0 Hz, 1H), 4.54 (d,
J¼12.0 Hz, 1H), 3.53 (s, 3H), 2.08 (s, 3H); 13C NMR (100 MHz, CDCl3)
Compound 7e. White solid, mp 132–133 ꢁC; 1H NMR (400 MHz,
d: 201.7, 168.1, 141.4, 141.0, 128.8, 128.6, 127.8, 127.5, 126.9, 126.8,
CDCl3)
d
; 8.04 (br s, 1H), 7.04 (d, J¼1.8 Hz, 1H), 7.25(dd, J¼7.0, 1.8 Hz,
64.9, 52.5, 50.8, 30.0.
1H), 7.16 (d, J¼8.4 Hz, 1H), 7.12 (d, J¼8.8 Hz, 4H), 6.84 (d, J¼8.8 Hz,
Compound 5i. White solid, 1H NMR (400 MHz, CDCl3)
d; 7.30–
4H), 6.54 (d, J¼1.8 Hz, 1H), 5.53 (s, 1H), 3.78 (s, 6H); 13C NMR
7.22 (m, 8H), 7.17–7.12 (m, 2H), 4.77 (d, J¼12.0 Hz, 1H), 4.52 (d,
(100 MHz, CDCl3) d: 157.9, 136.0, 135.2, 129.6, 128.6, 125.1, 124.8,
J¼12.0 Hz, 1H), 3.96 (q, J¼7.0 Hz, 4H), 2.08 (s, 3H), 0.98 (t, J¼7.0 Hz,
122.2, 120.1, 113.6, 112.5, 112.5, 55.1, 46.8; HRMS–FAB (m/z): [M]þ
calcd for C23H20BrNO2: 421.0677, found: 421.0677.
4H); 13C NMR (100 MHz, CDCl3)
d: 201.7, 167.6, 141.5, 141.2, 128.7,
128.5, 127.7, 127.6, 126.9, 126.7, 65.1, 61.4, 50.8, 29.9, 13.7.
Compound 7f. White solid, mp 166–167 ꢁC; 1H NMR (400 MHz,
Compound 5j. White solid, 1H NMR (400 MHz, CDCl3)
d; 7.43–
CDCl3)
7.06–7.02 (m, 2H), 6.90 (t, J¼8.4 Hz, 2H), 6.81 (d, J¼8.4 Hz, 4H), 5.64
(s, 1H), 3.74 (s, 6H), 2.12 (s, 3H); 13C NMR (100 MHz, CDCl3)
: 157.7,
d
; 7.72 (br s, 1H), 7.21 (d, J¼7.8 Hz, 1H), 7.12 (d, J¼8.4 Hz, 4H),
7.93 (m, 4H), 7.23–7.19 (m, 4H), 7.16–7.13 (m, 2H), 3.89–3.87 (m,1H),
3.80–3.76 (m, 1H), 2.65–2.58 (m, 1H), 2.45–2.32 (m, 2H), 1.89–1.82
(m, 1H), 1.77–1.64 (m, 2H), 1.57–1.42 (m, 2H), 0.89 (t, J¼7.0 Hz, 3H);
d
136.3, 135.1, 131.8, 129,7, 128.3, 120.6, 119.5, 119.0, 114.4, 113.5, 110.1,
55.2, 46.0, 12.3; HRMS–FAB (m/z): [M]þ calcd for C24H23NO2:
357.1729, found: 357.1729.
13C NMR (100 MHz, CDCl3)
d: 206.1, 170.5, 140.7, 140.4, 130.5, 130.1,
127.8, 126.4, 126.2, 65.7, 61.1, 54.0, 41.7, 34.7, 26.6, 22.6, 13.3.
Compound 5k. White solid, 1H NMR (400 MHz, CDCl3)
d
; 7.29 (d,
Compound 7g. White solid, mp 129–130 ꢁC; 1H NMR (400 MHz,
J¼7.0 Hz, 4H), 7.25–7.21 (m, 4H), 7.16–7.12 (m, 4H), 4.75 (d,
J¼12.0 Hz, 1H), 4.33 (d, J¼12.0 Hz, 1H), 4.19 (q, J¼7.0 Hz, 4H), 1.26 (t,
CDCl3)
4H), 6.73 (d, J¼2.5 Hz, 1H), 6.54 (d, J¼2.1 Hz, 1H), 5.58 (s, 1H), 3.81
(s, 6H), 3.73 (s, 3H); 13C NMR (100 MHz, CDCl3)
: 157.8,153.5,136.4,
d
; 7.93 (br s, 1H), 7.20 (d, J¼8.4 Hz, 4H), 6.88 (d, J¼8.8 Hz,
J¼7.0 Hz, 4H); 13C NMR (100 MHz, CDCl3)
d
: 167.5, 141.2, 128.4,
d
127.6, 126.7, 61.3, 57.3, 41.4, 13.8.
131.8, 129.7, 127.3, 124.6, 120.0, 113.5, 111.8, 111.7, 101.9, 55.7, 55.1,
47.0; EI (m/z): [M]þ calcd for C25H23NO4: 401.1627, found: 401.18,
400.16, 2677.09, 228.16, 227.12, 105.04.
Compound 5l. White solid, mp 98–99 ꢁC; 1H NMR (400 MHz,
CDCl3)
J¼12.0 Hz, 1H), 4.00 (q, J¼7.0 Hz, 4H), 2.11 (s, 3H), 1.04 (t, J¼7.0 Hz,
4H); 13C NMR (100 MHz, CDCl3)
: 200.8, 167.2, 139.6, 139.4, 133.0,
d; 7.26–7.15 (m, 8H), 4.73 (d, J¼12.0 Hz, 1H), 4.43 (d,
Compound 7h. White solid, mp 124–125 ꢁC; 1H NMR (400 MHz,
d
CDCl3)
d
; 7.30–7.26 (m, 4H), 7.22–7.20 (m, 2H), 7.12 (d, J¼7.4 Hz,