The Journal of Organic Chemistry
Article
HRMS (ESI)+ m/z calcd for C14H16NO4 [M + H]+ 262.1079, found
262.1074.
108.5, 66.6, 53.9, 21.4, 20.1; IR (NaCl) 2956, 2921, 2850, 1740 cm−1;
HRMS (ESI)+ m/z calcd for C14H16NO4 [M + H]+ 262.1079, found
262.1074.
Methyl 2-(Acetoxymethyl)-5-(tert-butyl)-1H-indole-1-carboxy-
late (6). Compound 6 was prepared on a 0.100 mmol scale with
methyl [4-methoxy-2-(propa-1,2-dien-1-yl)phenyl]carbamate (S31)
and lead tetraacetate using general procedure E. The product was
obtained as a white solid (21.3 mg, 72%): 1H NMR (500 MHz,
CDCl3) δ 8.04 (d, J = 8.9 Hz, 1H), 7.54 (d, J = 2.1 Hz, 1H), 7.41 (dd,
J = 8.8, 2.0 Hz, 1H), 6.66 (s, 1H), 5.47 (s, 2H), 4.05 (s, 3H), 2.14 (s,
3H), 1.39 (s, 9H); 13C{1H} NMR (126 MHz, CDCl3) δ 170.6, 152.1,
146.5, 134.9, 134.8, 128.7, 122.9, 117.1, 115.3, 111.4, 60.6, 53.8, 34.7,
31.8, 21.1; IR (NaCl) 2956, 2918, 2847, 1743, 1721 cm−1; HRMS
(ESI)+ m/z calcd for C17H22NO4 [M + H]+ 304.1549, found
304.1543.
Methyl 2-(1-Acetoxyethyl)-5-bromo-1H-indole-1-carboxylate
(22). Compound 22 was prepared on a 0.071 mmol scale with
methyl [4-bromo-2-(buta-1,2-dien-1-yl)phenyl]carbamate (18) and
lead tetraacetate using general procedure E. The product was
obtained as a white solid (11.6 mg, 48%): 1H NMR (500 MHz,
CDCl3) δ 8.00 (d, J = 8.9 Hz, 1H), 7.65 (s, 1H), 7.40 (d, J = 9.0 Hz,
1H), 6.65 (s, 1H), 6.51 (q, J = 6.5 Hz, 1H), 4.04 (s, 3H), 2.10 (s,
3H), 1.66 (d, J = 6.4 Hz, 3H); 13C{1H} NMR (126 MHz, CDCl3) δ
170.1, 151.8, 142.1, 135.5, 130.5, 127.7, 123.4, 117.4, 116.7, 107.5,
66.4, 54.2, 21.3, 20.2; IR (NaCl) 2959, 2926, 2844, 1740 cm−1;
HRMS (ESI)+ m/z calcd for C14H15BrNO4 [M + H]+ 340.0184,
found 340.0179.
Methyl 2-(Acetoxymethyl)-5-methoxy-1H-indole-1-carboxylate
(7). Compound 7 was prepared on a 0.187 mmol scale with methyl
[4-methoxy-2-(propa-1,2-dien-1-yl)phenyl]carbamate (S32) and lead
tetraacetate using general procedure E. The product was obtained as
Methyl 2-(2-Acetoxypropan-2-yl)-5-bromo-1H-indole-1-carbox-
ylate (24). Compound 24 was prepared on a 0.059 mmol scale
with methyl [4-bromo-2-(3-methylbuta-1,2-dien-1-yl)phenyl]-
carbamate (20) and lead tetraacetate using general procedure E.
1
an off-white solid (33.2 mg, 64%): H NMR (500 MHz, CDCl3) δ
1
7.99 (d, J = 9.1 Hz, 1H), 6.97 (d, J = 2.5 Hz, 1H), 6.92 (dd, J = 9.1,
2.6 Hz, 1H), 6.59−6.58 (m, 1H), 5.42 (d, J = 0.9 Hz, 2H), 4.01 (s,
3H), 3.83 (s, 3H), 2.13 (s, 3H); 13C{1H} NMR (126 MHz, CDCl3) δ
170.7, 156.4, 152.0, 135.6, 131.4, 129.7, 116.6, 113.7, 110.8, 103.3,
60.5, 55.6, 53.8, 20.9; IR (NaCl) 2956, 2921, 2853, 2833, 1737 cm−1;
HRMS (ESI)+ m/z calcd for C14H16NO5 [M + H]+ 278.1028, found
278.1023.
tert-Butyl 2-(Acetoxymethyl)-1H-indole-1-carboxylate (10).
Compound 10 was prepared on a 0.113 mmol scale with tert-butyl
[2-(propa-1,2-dien-1-yl)phenyl]carbamate (S34) and lead tetraace-
tate using general procedure E. The product was obtained as a white
solid (23.8 mg, 73%): 1H NMR (500 MHz, CDCl3) δ 8.16 (d, J = 8.4
Hz, 1H), 7.53 (d, J = 7.7 Hz, 1H), 7.35−7.28 (m, 1H), 7.23 (t, J = 7.5
Hz, 1H), 6.65 (s, 1H), 5.46 (s, 2H), 2.16 (s, 3H), 1.70 (s, 9H);
13C{1H} NMR (126 MHz, CDCl3) δ 170.6, 150.1, 136.9, 135.0,
128.7, 124.7, 123.0, 120.8, 115.8, 110.0, 84.5, 61.0, 31.0, 21.1; IR
(NaCl) 2981, 2935, 1738 cm−1; HRMS (ESI)+ m/z calcd for
C16H20NO4 [M + H]+ 290.1392, found 290.1387.
The product was obtained as a white solid (3 mg, 14%): H NMR
(500 MHz, CDCl3) δ 7.82 (d, J = 8.9 Hz, 1H), 7.63 (d, J = 2.1 Hz,
1H), 7.36 (dd, J = 8.9, 2.0 Hz, 1H), 6.61 (s, 1H), 4.06 (s, 3H), 2.03
(s, 3H), 1.92 (s, 6H); 13C{1H} NMR (126 MHz, CDCl3) δ 169.8,
152.0, 144.7, 136.1, 130.1, 127.4, 123.5, 117.0, 116.3, 108.0, 54.1,
28.3, 22.1; IR (NaCl) 2956, 2926, 2847, 1757, 1730 cm−1; HRMS
(ESI)+ m/z calcd for C15H17BrNO4 [M + H]+ 354.0341, found
354.0336.
Methyl 2-(Acetoxymethyl)-1H-indole-1-carboxylate-3-d (36).
Compound 36 was prepared on a 0.110 mmol scale with methyl
[2-(propa-1,2-dien-1-yl-1-d)phenyl]carbamate (35) and lead tetraa-
cetate using general procedure E. The product was obtained as a
white solid (18.7 mg, 68%): 1H NMR (500 MHz, CDCl3) δ 8.14 (dt,
J = 8.4, 0.9 Hz, 1H), 7.54 (dt, J = 7.7, 1.1 Hz, 1H), 7.34 (ddd, J = 8.5,
7.2, 1.4 Hz, 1H), 7.28−7.23 (m, 1H), 5.47 (s, 2H), 4.06 (s, 3H), 2.15
(s, 3H); 13C{1H} NMR (126 MHz, CDCl3) δ 170.7, 152.1, 136.8,
134.9, 128.8, 125.0, 123.5, 120.9, 115.8, 110.8 (t, J = 26.9 Hz), 60.6,
54.0, 21.1; IR (NaCl) 2960, 2921, 2853, 1746 cm−1; HRMS (ESI)+
m/z calcd for C13H13DNO4 [M + H]+ 249.0986, found 249.0980.
Methyl 2-[(Benzoyloxy)methyl]-1H-indole-1-carboxylate (13).
Compound 13 was prepared on a 0.108 mmol scale with methyl
[2-(propa-1,2-dien-1-yl)phenyl]carbamate (S27) and lead tetraben-
zoate using general procedure E. The product was obtained as a white
Benzyl 2-(Acetoxymethyl)-1H-indole-1-carboxylate (11). Com-
pound 11 was prepared on a 0.100 mmol scale with benzyl [2-(propa-
1,2-dien-1-yl)phenyl]carbamate (S35) and lead tetraacetate using
general procedure E. The product was obtained as a white solid (21.1
1
mg, 65%): H NMR (500 MHz, CDCl3) δ 8.14 (d, J = 8.3 Hz, 1H),
1
7.53−7.47 (m, 3H), 7.39 (dd, J = 10.4, 7.1 Hz, 3H), 7.32−7.25 (m,
1H), 7.25−7.19 (m, 1H), 6.66 (s, 1H), 5.45 (s, 2H), 5.42 (s, 2H),
2.02 (s, 3H); 13C{1H} NMR (126 MHz, CDCl3) δ 170.6, 151.4,
136.9, 130.4, 129.7, 129.0, 128.9, 128.8, 128.4, 125.0, 123.4, 120.9,
115.9, 111.2, 69.1, 60.7, 21.0; IR (NaCl) 2956, 2924, 2853, 1734
cm−1; HRMS (ESI)+ m/z calcd for C19H18NO4 [M + H]+ 324.1236,
found 324.1230.
2,2,2-Trichloroethyl 2-(Acetoxymethyl)-1H-indole-1-carboxylate
(12). Compound 12 was prepared on a 0.077 mmol scale with 2,2,2-
trichloroethyl [2-(propa-1,2-dien-1-yl)phenyl]carbamate (S36) and
lead tetraacetate using general procedure E. The product was
obtained as a white solid (14.9 mg, 56%): 1H NMR (500 MHz,
CDCl3) δ 8.26 (dq, J = 8.4, 0.9 Hz, 1H), 7.56−7.53 (m, 1H), 7.36
(ddd, J = 8.5, 7.2, 1.3 Hz, 1H), 7.31−7.27 (m, 1H), 6.74 (q, J = 1.0
Hz, 1H), 5.52 (d, J = 1.0 Hz, 2H), 5.10 (s, 2H), 2.14 (s, 3H);
13C{1H} NMR (126 MHz, CDCl3) δ 170.7, 150.1, 136.9, 135.2,
solid (20.1 mg, 57%): H NMR (500 MHz, CDCl3) δ 8.18 (dq, J =
8.4, 0.8 Hz, 1H), 8.12−8.09 (m, 2H), 7.60−7.56 (m, 1H), 7.54 (ddd,
J = 7.8, 1.3, 0.8 Hz, 1H), 7.48−7.44 (m, 2H), 7.35 (ddd, J = 8.5, 7.2,
1.3 Hz, 1H), 7.28−7.24 (m, 1H), 6.76 (q, J = 1.0 Hz, 1H), 5.72 (d, J
= 1.0 Hz, 2H), 4.03 (s, 3H); 13C{1H} NMR (126 MHz, CDCl3) δ
166.4, 152.2, 137.0, 135.1, 133.4, 130.2, 123.0, 129.0, 128.7, 125.1,
123.5, 121.0, 115.9, 111.0, 61.1, 54.0; IR (NaCl) 2956, 2926, 2855,
1743, 1724 cm−1; HRMS (ESI)+ m/z calcd for C18H16NO4 [M + H]+
310.1079, found 310.1074.
Methyl 2-{[(4-Fluorobenzoyl)oxy]methyl}-1H-indole-1-carboxy-
late (14). Compound 14 was prepared on a 0.159 mmol scale with
methyl [2-(propa-1,2-dien-1-yl)phenyl]carbamate (S27) and lead
tetra(4-fluorobenzoate) using general procedure E. The product was
obtained as a white solid (22.8 mg, 44%): 1H NMR (500 MHz,
CDCl3) δ 8.17 (d, J = 8.4 Hz, 1H), 7.55 (dd, J = 7.7, 1.2 Hz, 1H),
7.36 (ddd, J = 8.5, 7.3, 1.4 Hz, 1H), 7.18−7.06 (m, 3H), 6.76 (d, J =
1.1 Hz, 1H), 5.71 (d, J = 1.1 Hz, 2H), 4.04 (s, 3H); 13C{1H} NMR
(126 MHz, CDCl3) δ 166.2 (d, J = 223.9 Hz), 165.0, 152.1, 136.9,
134.8, 132.4 (d, J = 9.5 Hz), 128.9, 126.4 (d, J = 2.9 Hz), 125.1,
121.0, 115.9 (d, J = 3.0 Hz), 115.7, 111.2, 61.2, 54.0; 19F NMR (376
MHz, CDCl3) δ −105.30; IR (NaCl) 2956, 2924, 2853, 1741, 1724
cm−1; HRMS (ESI)+ m/z calcd for C18H15FNO4 [M + H]+ 328.0985,
found 328.0980.
129.2, 125.5, 124.1, 121.2, 116.2, 112.2, 94.3, 76.3, 60.6, 21.0; IR
(NaCl) 2959, 2924, 2850, 1734 cm−1; HRMS (ESI)+ m/z calcd for
C14H13Cl3NO4 [M + H]+ 363.9910, found 363.9905.
Methyl 2-(1-Acetoxyethyl)-1H-indole-1-carboxylate (23). Com-
pound 23 was prepared on a 0.197 mmol scale with methyl [2-(buta-
1,2-dien-1-yl)phenyl]carbamate (19) and lead tetraacetate using
general procedure E. The product was obtained as a colorless oil
1
(25 mg, 49%): H NMR (500 MHz, CDCl3) δ 8.12 (d, J = 8.4 Hz,
Methyl 2-({[4-(Trifluoromethyl)benzoyl]oxy}methyl)-1H-indole-
1-carboxylate (16). Compound 16 was prepared on a 0.159 mmol
scale with methyl [2-(propa-1,2-dien-1-yl)phenyl]carbamate (S27)
and lead tetra(4-trifluoromethylbenzoate) using general procedure E.
The product was obtained as a white solid (32.4 mg, 54%): 1H NMR
1H), 7.55−7.49 (m, 1H), 7.31 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 7.27−
7.20 (m, 1H), 6.72 (s, 1H), 6.53 (q, J = 6.4 Hz, 1H), 4.03 (s, 3H),
2.09 (s, 3H), 1.66 (d, J = 6.5 Hz, 3H); 13C{1H} NMR (126 MHz,
CDCl3) δ 170.2, 152.1, 140.6, 136.8, 128.8, 124.9, 123.4, 120.8, 115.9,
10721
J. Org. Chem. 2021, 86, 10713−10723