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H3); 5.00 (2 H, p, J = 7.2 Hz, Hα); 4.19−4.05 (m, 4 H, R2); 1.67−
1.50 (m, 4 H, R2); 1.45−1.24 (m, 10 H, R2); 0.89 (6 H, t, J = 7.4
Hz, R1). 13CNMR (126 MHz, DMSO-d6) δ: 182.0; 172.6; 134.8;
132.1; 127.8; 127.1; 126.4; 125.4; 123.8; 116.7; 64.2; 52.8; 30.1;
18.6; 17.5; 13.5. HRMS: calcd for C30H38N4O4S2 + H 583.2413,
found 583.2406. Anal. Calcd for C30H38N4O4S2: C, 61.83; H, 6.57;
N, 9.61; S, 11.00. Found: C, 61.97; H, 6.51; N, 9.48; S, 10.91. O.R.:
[α]2D0 = −83.3 (c = 0.475, DCM).
C40H42N4O4S2: C, 67.96; H, 5.99; N, 7.93; S, 9.07. Found: C, 67.90;
H, 6.07; N, 7.92; S, 9.05. O.R.: [α]2D0 = −141 (c = 0.5; DCM).
1i. Yellow powder. Yield: 292 mg (45%). Mp: 107−110 °C.
1HNMR (500 MHz, DMSO-d6) δ: 10.05 (s, 2 H, Ha); 8.71 (s, 1 H,
H10); 8.70 (s, 1 H, H9); 8.02 (2 H, d, J = 8.5 Hz, H2); 7.89 (2 H, d,
J = 7.7 Hz, Hb); 7.57−7.45 (m, 2 H, R1); 7.41 (2 H, d, J = 7.0 Hz,
H4); 7.37−7.08 (m, 10 H, H3 + R1); 5.60−4.90 (m, 2 H, Hα);
3.69(s, 6 H, R2); 3.17−3.08 (m, 4 H, R1). 13CNMR (126 MHz,
DMSO-d6) δ: 182.1; 171.7; 136.5; 134.6; 132.1; 129.2; 128.3; 127.8;
127.2; 126.6; 126.5; 125.4; 123.8; 116.5; 58.3; 51.9; 37.1. HRMS:
calcd for C36H34N4O4S2 + H 651.2100, found 651.2087. Anal. Calcd
for C36H34N4O4S2: C, 66.44; H, 5.27; N, 8.61; S, 9.85. Found: C,
66.49; H, 5.54; N, 8.35; S, 9.75. O.R.: [α2D0] = −168.3 (c = 0.485;
DCM).
1j. Yellow powder. Yield: 177 mg (25%). Mp: 101−103 °C.
1HNMR (500 MHz, DMSO-d6) δ: 10.07 (s, 2 H, Ha); 8.73 (s, 1 H,
H10); 8.70 (s, 1 H, H9); 8.03 (2 H, d, J = 7.6 Hz H2); 7.80 (2 H, d,
J = 7.9 Hz, H4); 7.55−7.47 (m, 4 H, H4 + R1); 7.40−7.09 (m, 10 H,
H3 + R1); 5.25−5.17 (m, 2 H, R2); 4.96−4.75 (m, 2 H, Hα); 3.17 (2
H, dd, J = 13.5; 5.9 Hz, R1); 3.09 (2 H, dd, J = 13.5; 7.1 Hz, R1);
1.13 (6 H, d, J = 6.2 Hz, R2); 1.05 (6 H, d, J = 6.2 Hz, R2).
13CNMR (126 MHz, DMSO-d6) δ: 181.9; 170.6; 136.5; 134.6;
132.1; 129.2; 128.3; 127.8; 127.2; 126.6; 126.5; 125.4; 123.8; 116.5;
68.3; 58.2; 37.2; 21.4; 21.3. HRMS: calcd for C40H42N4O4S2 + H
707.2726, found 707.2726. Anal. Calcd for C40H42N4O4S2: C, 67.96;
H, 5.99; N, 7.93; S, 9.07. Found: C, 67.74; C, 6.17; N, 7.83; S, 9.16.
O.R.: [α]2D0 = −129.3 (c = 0.55; DCM).
1k. Yellow powder. Yield: 257 mg (35%). Mp: 71−75 °C.
1HNMR (500 MHz, DMSO-d6) δ: 10.07 (s, 2 H, Ha); 8.72 (s, 1 H,
H10); 8.70 (s, 1 H, H9); 8.03 (2 H, d, J = 8.5 Hz, H2); 7.82 (2 H, d,
J = 7.6 Hz, H4); 7.56−7.48 (m, 2 H, R1); 7.45 (2 H, d, J = 7.0 Hz,
Hb); 7.30−7.17 (m, 6 H, R1); 7.13 (4 H, m, H3 + R1); 5.30−5.23
(m, 2 H, Hα); 4.04−3.92 (m, 4 H, R2); 3.16 (2 H, dd, J = 13.8; 6.2
Hz, R1); 3.09 (2 H, dd, J = 13.6; 6.9 Hz, R1); 1.49−1.40 (m, 4 H,
R2); 1.25−1.16 (m, 4 H, R2); 0.82 (6 H, t, J = 7.4 Hz, R2). 13CNMR
(126 MHz, DMSO-d6) δ: 182.4; 171.7; 136.9; 135.1; 132.5; 129.6;
128.7; 128.2; 127.7; 127.1; 127.0; 125.8; 124.3; 117.0; 64.8; 58.8;
37.7; 30.4; 18.9; 14.0. HRMS: calcd for C42H46N4O4S2 + H
735.3039, found: 735.3034. Anal. Calcd for C42H46N4O4S2: C, 68.64;
H, 6.31; N, 7.62; S, 8.73. Found: C, 68.45; H, 6.50; N, 7.54; S, 8.80.
O.R.: [α]2D0 = 136.9 (c = 0.55; DCM).
1d. Yellow powder. Yield: 240 mg (37%). Mp: 99−101 °C.
1HNMR (500 MHz, DMSO-d6) δ: 9.93 (s, 2 H, Ha); 8.68 (s, 1 H,
H10); 8.67 (s, 1 H, H9); 8.15 (2 H, d, J = 7.3 Hz, H2); 8.01 (2 H, d,
J = 8.4 Hz, H4); 7.56 (2 H, d, J = 6.9 Hz, Hb); 7.53−7.46 (m, 2 H,
H3); 7.45−7.28 (m, 10 H, R2); 5.17 (4 H, s, R2); 5.14−4.95 (m, 2
H, Hα); 1.40 (6 H, d, J = 7.2 Hz, R1). 13CNMR (126 MHz, DMSO-
d6) δ: 182.5; 172.9; 136.4; 135.3; 132.5; 128.9; 128.5; 128.3; 128.3;
127.5; 126.9; 125.9; 124.2; 117.1; 66.5; 53.4; 17.8. HRMS: calcd for
C36H34N4O4S2 + H 651.2100, found 651.2100. Anal. Calcd for
C36H34N4O4S2: C, 66.44; H, 5.27; N, 8.61; S, 9.85. Found: C, 66.45;
H, 5.36; N, 8.34; S, 9.70. O.R.: [α]2D0 = −89.45 (c = 0.45; DCM).
1e. Yellow powder. Yield: 250 mg (45%). Mp: 177−179 °C.
1HNMR (500 MHz, DMSO-d6) δ: 10.05 (s, 2 H, Ha); 8.73 (s, 1 H,
H10); 8.68 (s, 1 H, H9); 8.08 (2 H, d, J = 7.6 Hz, H4); 7.99 (2 H, d,
J = 8.5 Hz, H2); 7.80 (2 H, d, J = 7.0 Hz, Hb); 7.54 (2 H, t, J = 7.8
Hz, H3); 4.95 (2 H, dd, J = 7.6; 5.3 Hz, Hα); 3.70 (s, 6 H); 2.26−
2.15 (m, 2 H); 0.98 (12 H, s, J = 6.7 Hz). 13CNMR (126 MHz,
DMSO-d6) δ: 182.7; 171.9; 134.9; 131.9; 127.5; 127.3; 125.9; 125.2;
123.4; 115.4; 62.0; 51.7; 30.6; 18.7; 18.5. HRMS: calcd for
C28H34N4O4S2 555.2100, found 555.2096. Anal. Calcd for
C28H34N4O4S2: C, 60.62; H, 6.18; N, 10.10; S, 11.56. Found: C,
60.55; H, 6.09; N, 9.95; S, 11.62. O.R.: [α]2D0 = −220 (c = 0.55;
DCM).
1f. Yellow powder. Yield: 183 mg (30%). Mp: 200−204 °C.
1HNMR (500 MHz, DMSO-d6) δ: 10.08 (s, 2 H, Ha); 8.74 (s, 1 H,
H10); 8.68 (s, 1 H, H9); 8.06−7.86 (m, 4 H, H2 + H4); 7.81 (2 H, d,
J = 7.1 Hz, Hb); 7.54 (2 H, t, J = 7.8 Hz), H3; 5.07−4.92 (m, 2 H,
R2); 4.88 (2 H, dd, J = 7.7; 5.0 Hz, Hα); 2.31−2.15 (m, 2 H, R1);
1.24 (6 H, d, J = 6.6 Hz, R2); 1.23 (6 H, d, J = 6.8 Hz, R2); 1.00−
0.93 (12 H, m, J = 6.7 Hz, R1). 13CNMR (126 MHz, DMSO-d6) δ:
182.5; 170.7; 134.9; 131.9; 127.5; 127.3; 125.8; 125.2; 123.3; 115.4;
68.1; 61.9; 30.6; 21.6; 21.5; 18.58; 18.58. HRMS: calcd for
C32H42N4O4S2 + H 611.2726, found 611.2733. Anal. Calcd for
C32H42N4O4S2: C, 62.92; H, 6.93; N, 9.17; S, 10.50. Found: C,
63.08; H, 7.00; N, 9.16; S, 10.56. O.R.: [α]2D0 = −159.5 (c = 0.485;
DCM).
1g. Yellow powder. Yield: 185 mg (29%). Mp: 173−175 °C.
1HNMR (500 MHz, DMSO-d6) δ: 10.07 (s, 2 H, Ha); 8.73 (s, 1 H,
H10); 8.68 (s, 1 H, H9); 8.07−7.92 (m, 4 H, H2 + H4); 7.80 (2 H, d,
J = 7.1 Hz, Hb); 7.54 (2 H, t, J = 7.8 Hz, H3); 4.93 (2 H, dd, J =
7.8; 5.2 Hz, Hα); 4.29−3.90 (m, 4 H, R2); 2.27−2.14 (m, 2 H, R1);
1.74−1.52 (m, 4 H, R2); 1.41−1.32 (m, 4 H, R2); 0.97 (12 H, d, J =
6.9 Hz, R1); 0.90 (6 H, t, J = 7.4 Hz, R2). 13CNMR (126 MHz,
DMSO-d6) δ: 182.6; 171.3; 134.8; 131.9; 127.5; 127.3; 125.8; 125.2;
123.3; 115.4; 64.1; 62.0; 30.6; 30.1; 18.7; 18.6; 18.4; 13.4. HRMS:
calcd for C34H46N4O4S2 + H 639.3027, found 639.3050. Anal. Calcd
for C34H46N4O4S2: C, 63.92; H, 7.26; N, 8.77; S, 10.04. Found: C,
63.65; H, 7.06; N, 8.68; S, 10.15. O.R.: [α]2D0 = −172.0 (c = 0.62;
DCM).
1h. Yellow powder. Yield: 148 mg (21%). Mp: 153−156 °C.
1HNMR (500 MHz, DMSO-d6) δ: 10.08 (s, 2 H, Ha); 8.73 (s, 1 H,
H10); 8.68 (s, 1 H, H9); 8.08 (2 H, d, J = 7.7 Hz, H2); 7.99 (2 H, d,
J = 8.5 Hz, H4); 7.79 (2 H, d, J = 7.0 Hz, Hb); 7.63−7.48 (m, 2 H,
H3); 7.48−7.30 (m, 10 H, R2); 5.22 (2 H, d, J = 12.4 Hz, R2); 5.17
(2 H, d, J = 12.4 Hz, R2); 4.98 (2 H, dd, J = 7.7; 5.2 Hz, Hα); 2.27−
2.15 (m, 2 H, R1); 0.96 (6 H, d, J = 7.1 Hz, R1); 0.94 (6 H, d, J =
7.1 Hz, R1). 13CNMR (126 MHz, DMSO-d6) δ: 182.7; 171.2; 135.8;
134.8; 131.9; 128.4; 128.09; 128.05; 127.5; 127.3; 127.1; 125.8;
125.2; 123.3; 115.5; 66.0; 62.1; 30.6; 18.7; 18.4. HRMS: calcd for
C40H42N4O4S2 + H 707.2726, found 707.2706. Anal. Calcd for
1l. Yellow powder. Yield: 297 mg (37%). Mp: 99−101 °C.
1HNMR (500 MHz, DMSO-d6) δ: 10.05 (s, 2 H, Ha); 8.71 (s, 1 H,
H10); 8.70 (s, 1 H, H9); 8.02 (2 H, d, J = 8.5 Hz, H2); 7.89 (2 H, d,
J = 7.7 Hz, Hb); 7.57−7.45 (m, 2 H, R1); 7.41 (2 H, d, J = 7.0 Hz,
H4); 7.37−7.08 (m, 10 H, H3 + R1); 5.22 (2 H, d, J = 12.4 Hz, R2);
5.17 (2 H, d, J = 12.4 Hz, R2); 5.10−4.90 (m, 2 H, Hα); 3.69(s, 6 H,
R2); 3.17−3.08 (m, 4 H, R1). 13CNMR (100 MHz, DMSO-d6) δ:
181.8; 171.6; 137.7; 137.1; 135.6; 135.4; 129.4; 129.1; 128.3; 128.2;
127.2; 124.6; 123.4; 120.4; 119.7; 116.2; 66.7; 55.8; 37.6. HRMS:
calcd for C48H42n4O4S2 + H 803.2726, found 803.2715. O.R.: [α]D20
−149.8 (c = 0.46; DCM).
=
1m. Yellow powder. Yield: 240 mg (37%). Mp: 154−157 °C.
1HNMR (500 MHz, DMSO-d6) δ: 10.87 (s, 2 H, Ha); 10.07 (s, 2 H,
R1); 8.74 (s, 1 H, H10); 8.68 (s, 1 H, H9); 8.00 (2 H, d, J = 7.7 Hz,
Hb); 7.84 (2 H, d, J = 6.5 Hz, H4); 7.53−7.40 (m, 6 H, R1 + H3);
7.34 (2 H, d, J = 8.0 Hz); 7.12−6.98 (m, 4 H, R1); 6.93 (2 H, t, J =
7.3 Hz, R1); 5.37−5.28 (m, 2 Hα); 3.31 (s, 4 H, R1). 13CNMR (126
MHz, DMSO-d6) δ: 181.9; 172.1; 136.0; 134.7; 132.0; 127.7; 127.2;
127.1; 126.3; 125.3; 123.9; 123.6; 121.0; 118.4; 118.1; 116.4; 111.4;
108.6; 57.8; 51.9; 27.2. HRMS: calcd for C40H36N4O4S2 + H
729.2318, found 729.2315. Anal. Calcd for C40H36N6O4S2: C, 65.91;
H, 4.98; N, 11.53; S, 8.80. Found: C, 65.00; H, 5.15; N, 11.14; S,
8.63.
Competitive titrations47 were conducted in MeCN-d3 (0.05%
H2O, Eurisotop, packed in vial with septum) on a mixture of chiral
host (∼0.01 M) and achiral reference 9 (∼0.005 M); the differences
in concentrations enabled unambiguous assignment of signals. To
this mixture were added aliquots of solution of homochiral guest in
G
J. Org. Chem. XXXX, XXX, XXX−XXX