The Journal of Organic Chemistry
NOTE
2.80 (s, 3H), 1.72 (d, J = 6.6 Hz, 3H), 1.40 (s, 9H); minor δ 8.26 (br,
1H), 7.32ꢀ6.86(m, 4H), 5.18ꢀ5.08 (m, 1H), 4.82 (d, J = 10.0 Hz, 1H),
2.82 (s, 3H), 1.46 (d, J = 6.6 Hz, 3H), 1.36 (s, 9H); 13C NMR (125 MHz,
CDCl3) major δ 170.3, 136.0, 130.5, 125.0, 122.7, 122.5, 122.3, 109.7,
109.5, 86.1, 82.4, 48.4, 27.9, 20.6, 18.2; minor δ 171.2, 136.2, 130.4, 125.0,
122.8, 122.5, 122.2, 110.2, 109.8, 85.5, 82.1, 47.3, 27.8, 21.1, 18.3; HRMS
calcd for C17H22O4N2Na (M þ Na)þ 341.1472, found m/z 341.1467;
enantiomeric excess was determined by HPLC with a Chiralcel OD-H þ
Chiralpak AS-H column (90:10 hexane/2-propanol, 1.0 mL/min, 254 nm);
major: minor enantiomer tR = 14.9 min, major enantiomer tR = 16.9 min;
76% ee; minor: minor enantiomer tR = 13.5 min, major enantiomer tR =
20.5 min; 84% ee; [R]21.8D = þ138.8 (c=1.0, CHCl3, d.r.=52/48, 76% ee/
Entry 10, Table 2: yellow oil; 1H NMR (500 MHz, CDCl3) major δ
8.13 (br, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.22 (d, J = 2.6 Hz, 1H),
7.08ꢀ7.05 (m, 1H), 6.99 (d, J = 7.2 Hz, 1H), 5.27ꢀ5.21 (m, 1H), 4.40
(d, J = 9.7 Hz, 1H), 2.43 (s, 3H), 1.71 (d, J = 6.6 Hz, 3H), 1.42 (s, 9H);
minor δ 8.20 (br, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.22 (d, J = 2.6 Hz, 1H),
7.10ꢀ7.03 (m, 1H), 6.99 (d, J = 7.2 Hz, 1H), 5.27ꢀ5.21 (m, 1H), 4.35
(d, J = 10.6 Hz, 1H), 2.48 (s, 3H), 1.40 (d, J = 6.9 Hz, 3H), 1.38 (s, 9H);
13C NMR (125 MHz, CDCl3) major δ 169.8, 135.9, 128.5, 126.0, 123.3,
120.9, 120.5, 116.9, 109.4, 85.2, 82.7, 49.1, 28.2, 18.2, 16.7; minor
δ 169.8, 136.1, 128.5, 126.0, 123.3, 121.1, 120.7, 117.1, 109.4, 84.0, 82.7,
49.1, 28.1, 18.7, 16.7; HRMS calcd for C17H22O4N2Na (M þ Na)þ
341.1472, found: m/z 341.1466; enantiomeric excess was determined by
HPLC with a Chiralcel OD-H þ Chiralpak AS-H column (95:5 hexane/
84% ee); IR (neat) 3404, 2978, 1720, 1549, 1455, 1359 cmꢀ1
.
1
Entry 7, Table 2: yellow solid; H NMR (500 MHz, CDCl3) major
2-propanol, 1.0 mL/min, 254 nm); major: minor enantiomer tR
=
31.8 min, major enantiomer tR = 34.7 min; 67% ee; [R]22.0D = þ49.8
δ 8.08 (br, 1H), 7.48 (s, 1H), 7.27ꢀ7.17 (m, 2H), 7.02 (m, 1H), 5.26ꢀ
5.19 (m, 1H), 4.39 (d, J = 9.5 Hz, 1H), 2.46 (s, 3H), 1.71 (d, J = 6.6 Hz,
3H), 1.42 (s, 9H); minor δ 8.13 (br, 1H), 7.48 (s, 1H), 7.27ꢀ7.17 (m,
2H), 7.06 (m, 1H), 5.26ꢀ5.19 (m, 1H), 4.33 (d, J = 10.9 Hz, 1H), 2.47
(s, 3H), 1.40 (d, J = 6.6 Hz, 3H), 1.38 (s, 9H); 13C NMR (125 MHz,
CDCl3) major δ 169.3, 134.4, 129.3, 126.5, 124.2, 123.5, 118.6, 111.1,
108.3, 85.0, 82.5, 48.7, 28.0, 21.7, 17.9; minor δ 170.5, 134.7, 129.2,
126.5, 124.4, 123.5, 118.7, 111.3, 108.3, 83.8, 82.3, 48.3, 27.9, 21.7, 18.6;
HRMS calcd for C17H22O4N2Na (M þ Na)þ 341.1472, found m/z
341.1466; enantiomeric excess was determined by HPLC with a Chiralpak
AD-H column (90:10 hexane/2-propanol, 1.0 mL/min, 254 nm); major:
minor enantiomer tR = 8.4 min, major enantiomer tR = 9.2 min; 87% ee;
minor: minor enantiomer tR = 7.2 min, major enantiomer tR = 12.5 min;
(c = 1.0, CHCl3, dr = 91/9, 67% ee/ND); IR (neat) 3414, 2979, 1720,
1550, 1455, 1367 cmꢀ1
.
Entry 11, Table 2: yellow oil; 1H NMR (500 MHz, CDCl3) major δ
8.24 (br, 1H), 7.72 (t, J = 7.45 Hz, 1H), 7.40 (d, J = 8.02 Hz, 1H), 7.26ꢀ
7.13 (m, 3H), 5.26ꢀ5.17 (m, 1H), 4.44 (d, J = 10.9 Hz, 1H), 4.23ꢀ4.02
(m, 2H), 2.17ꢀ2.00 (m, 1H), 1.82ꢀ1.66 (m, 1H), 1.21 (t, J = 6.9 Hz,
3H), 0.87 (t, J = 7.5 Hz, 3H); minor δ 8.16 (br, 1H), 7.72 (t, J = 7.45 Hz,
1H), 7.33 (d, J = 8.02 Hz, 1H), 7.26ꢀ7.13 (m, 3H), 5.26ꢀ5.17 (m, 1H),
4.53 (d, J = 10.9 Hz, 1H), 4.23ꢀ4.02 (m, 2H), 2.17ꢀ2.00 (m, 1H),
1.82ꢀ1.66 (m,1H), 1.16 (t, J = 7.5 Hz, 3H), 1.04 (t, J = 6.9 Hz, 3H); 13C
NMR (125 MHz, CDCl3, diastereomixture) δ 171.4, 170.7, 136,4, 136,1,
126.0(2C), 123.6(2C), 122.9, 122.7, 120.5, 120.3, 119.1(2C), 111.7, 111.5,
108.5, 108.2, 91.5, 89.3, 61.7(2C), 47.2, 45.8, 31.7, 26.3, 25.1, 22.7, 10.5,
9.6; HRMS calcd for C15H18O4N2Na (M þ Na)þ 313.1159, found m/z
313.1154; enantiomeric excess was determined by HPLC with a Chiralpak
AS-H column (90:10 hexane/2-propanol, 1.0 mL/min, 254 nm); major:
major enantiomer tR = 11.7 min, minor enantiomer tR = 12.9 min; 87% ee;
minor: minor enantiomer tR = 8.5 min, major enantiomer tR = 9.4 min;
65% ee; [R]25.1D = þ65.1 (c = 1.0, CHCl3, dr = 51/49, 88% ee/81% ee);
[R]21.5 = þ75.5 (c = 1.0, CHCl3, dr = 89/11, 87% ee/78% ee); IR
D
(neat) 3410, 2979, 1721, 1550, 1455, 1367 cmꢀ1
.
Entry 8, Table 2: yellow solid; 1H NMR (500 MHz, CDCl3) major δ
8.14 (br, 1H), 7.27ꢀ7.11 (m, 3H), 6.84 (dd, J = 8.6, 2.3 Hz, 1H), 5.25ꢀ
5.19 (m, 1H), 4.39 (d, J = 9.7 Hz, 1H), 3,87 (s, 3H), 1.72 (d, J = 6.6 Hz,
3H), 1.42 (s, 9H); minor δ 8.21 (br, 1H), 7.27ꢀ7.11 (m, 3H), 6.88 (dd,
J = 8.8, 2.3 Hz, 1H), 5.25ꢀ5.19 (m, 1H), 4.32 (d, J = 10.0 Hz, 1H), 3,86
(s, 3H), 1.40(d, J = 7.2 Hz, 3H), 1.39 (s, 9H); 13C NMR (125 MHz,
CDCl3) major δ 169.6, 154.4, 131,2, 126.7, 124.0, 112.9, 112.2, 108.5,
100.6, 84.9, 82.5, 55.9, 48.7, 28.0, 18.1; minor δ 169.6, 154.4, 131,2,
126.7, 124.2, 113.2, 112.4, 108.3, 100.6, 84.9, 82.4, 55.9, 48.7, 27.9, 18.5;
HRMS calcd for C17H22O5N2Na (M þ Na)þ 357.1421, found m/z
357.1414; enantiomeric excess was determined by HPLC with a
Chiralcel OD-H þ Chiralpak AD-H column (90:10 hexane/2-propanol,
0.8 mL/min, 254 nm); major: major enantiomer tR = 30.7 min, minor
enantiomer tR = 43.1 min; 87% ee; minor: minor enantiomer tR = 43.1
min, minor enantiomer tR = 44.8 min; 65% ee; [R]24.9D = þ85.9 (c = 1.0,
CHCl3, dr = 90/10, 87% ee/65% ee); IR (neat) 3423, 2986, 1724, 1554,
IR (neat) 3414, 2979, 1729, 1552, 1458, 1374 cmꢀ1
.
Entry 12, Table 2: yellow solid; 1H NMR (500 MHz, CDCl3) major δ
8.24 (br, 1H), 7.91ꢀ7.07 (m, 10H), 6.27 (d, J = 11.7 Hz, 1H), 5.12 (d,
J = 11.7 Hz, 1H), 3.97ꢀ3.84 (m, 2H), 0.95 (t, J = 7.2 Hz, 3H); minor δ
8.02 (br, 1H), 7.91ꢀ7.07 (m, 10H), 7.27 (d, J = 11.7 Hz, 1H), 4.97 (d,
J = 11.5 Hz, 1H), 4.30ꢀ4.23 (m, 1H), 4.15ꢀ4.09 (m, 1H), 1.22 (t, J =
7.2 Hz, 3H); 13C NMR (125 MHz, CDCl3) major δ 169.7, 136.2, 132.9,
130.5, 129.1, 128.4, 126.1, 123.6, 122.8, 120.4, 119.3, 111.6, 108.6, 92.5,
61.5, 47.7, 13.8; minor δ 169.7, 136.2, 132.9, 130.5, 128.9, 127.7, 126.1,
124.0, 122.6, 120.3, 119.0, 111.5, 108.6, 90.2, 62.0, 47.6, 14.1; HRMS
calcd for C19H18O4N2Na (M þ Na)þ 361.1159, found m/z 361.1153;
enantiomeric excess was determined by HPLC with a Chiralpak AD-H
column (90:10 hexane/2-propanol, 1.0 mL/min, 254 nm); major: major
enantiomer tR = 33.6 min, minor enantiomer tR = 37.0 min; 66% ee;
minor: minor enantiomer tR = 20.4 min, major enantiomer tR = 22.8
min; 75% ee; [R]25.1D = þ114.8 (c = 1.0, CHCl3, dr = 77/23, 66% ee/
1457, 1368, 1153 cmꢀ1
.
Entry 9, Table 2: yellow solid; 1H NMR (500 MHz, CDCl3) major δ
8.20 (br, 1H), 7.86 (d, J = 1.7 Hz, 1H), 7.27 (dd, J = 10.3, 1.7 Hz, 1H),
7.20 (s, 1H), 7.20 (d, J = 10.3 Hz, 1H), 5.25ꢀ5.19 (m, 1H), 4.30 (d, J =
9.7 Hz, 1H), 1.71 (d, J = 6.6 Hz, 3H), 1.42 (s, 9H); minor δ 8.25 (br,
1H), 7.85 (d, J = 1.7 Hz, 1H), 7.32 (dd, J = 9.1, 1.7 Hz, 1H), 7.26 (d, J =
9.1 Hz, 1H), 7.20 (m, 1H), 5.24ꢀ5.18 (m, 1H), 4.30 (d, J = 10.6 Hz,
1H), 1.40 (d, J = 7.2 Hz, 3H), 1.38 (s, 9H); 13C NMR (125 MHz,
CDCl3) major δ 169.2, 134.7, 127.8, 125.5, 124.7, 121.7, 113.5, 113.0,
108.5, 84.8, 82.9, 48.9, 28.0, 18.2; minor δ 170.0, 135.0, 127.8, 125.8,
124.7, 121.8, 113.7, 113.2, 108.2, 83.4, 82.8, 48.2, 27.9, 18.5; HRMS calcd
for C16H19O4N2BrNa (M þ Na)þ 405.0420, found m/z 405.0411;
enantiomeric excess was determined by HPLC with a Chiralcel OD-H þ
OD-H column (90:10 hexane/2-propanol, 1.0 mL/min, 254 nm);
major: major enantiomer tR = 18.4 min, minor enantiomer tR = 22.0 min;
90% ee; minor: minor enantiomer tR = 17.3 min, major enantiomer tR =
19.5 min; 70% ee; major [R]25.0D = þ70.2 (c = 1.0, CHCl3, major only,
90% ee); minor [R]25.0D = þ56.8 (c = 1.0, CHCl3, minor only, 70% ee);
75% ee); IR (neat) 3412, 3062, 1728, 1554, 1457, 1368 cmꢀ1
.
Entry 1, Table 3: yellow oil; 1H NMR (500 MHz, CDCl3) major δ 8.70
(br, 1H), 6.75ꢀ6.74 (m, 1H), 6.13ꢀ6.11 (m, 1H), 6.10ꢀ6.08 (m, 1H),
5.08ꢀ5.02 (m, 1H), 4.28ꢀ4.10 (m, 1H), 1.60 (d, J = 6.6 Hz, 3H), 1.28
(t, J = 7.2 Hz, 3H); minor δ8.47 (br, 1H), 6.77ꢀ6.76 (m,1H), 6.17ꢀ
6.15 (m, 1H), 6.13ꢀ6.11 (m, 1H), 5.08ꢀ5.02 (m, 1H), 4.28ꢀ4.10 (m,
3H), 1.43 (d, J= 6.9 Hz, 3H), 1.23 (t, J= 7.2 Hz, 3H); 13C NMR (125 MHz,
CDCl3) major δ 169.9, 122.3, 119.1, 109.1, 108.8, 85.1, 62.2, 49.1, 17.7,
14.1; minor δ 169.9, 121.2, 119.2, 109.2, 108.8, 83.5, 62.2, 49.0, 17.8,
14.0; HRMS calcd for C10H14O4N2Na (M þ Na)þ 249.0846, found m/z
249.0845; enantiomeric excess was determined by HPLC with a
Chiralpak AD-Hþ Chiralcel OD-H column (98:2 hexane/2-propanol,
0.8 mL/min, 254 nm); major: minor enantiomer tR = 55.4 min, major
enantiomer tR = 64.6 min; 87% ee; minor: minor enantiomer tR = 53.0 min,
IR (neat) 3421, 1717, 1556, 1456, 1362, 1154 cmꢀ1
.
5454
dx.doi.org/10.1021/jo200546a |J. Org. Chem. 2011, 76, 5450–5456