FULL PAPERS
Iron-Catalyzed Dioxygenation of Alkenes and Terminal Alkynes
1
787, 1044, 1240, 1371, 1744, 2956 cmÀ1; H NMR (300 MHz,
CDCl3): d=2.06 (s, 3H), 2.12 (s, 3H), 3.81 (s, 3H), 4.27 (dd,
1H, J=8.0, 11.9 Hz), 4.33 (dd, 1H, J=3.8, 12.0 Hz), 5.98
(dd, 1H, J=3.6, 8.0 Hz), 6.84–6.92 (m, 2H), 6.95 (d, 1H, J=
7.6 Hz), 7.29 (d, 1H, J=7.9 Hz); 13C NMR (75 MHz,
CDCl3): d=20.7, 21.0, 55.2, 66.1, 73.2, 112.4, 113.8, 118.8,
129.7, 138.0, 159.7, 170.0, 170.6; ESI-MS: m/z=275 (M+
Na)+; ESI-HR-MS: m/z=275.08858 (M+Na)+, calcd. for
C13H16O5Na: 275.08899.
3H, J=6.9 Hz), 1.25–1.32 (m, 8H), 1.54–1.60 (m, 2H), 2.063
(s, 3H), 2.068 (s, 3H), 4.03 (dd, 1H, J=6.7, 11.9 Hz), 4.22
(dd, 1H, J=3.2, 11.9 Hz), 5.04–5.10 (m, 1H); 13C NMR
(75 MHz, CDCl3): d=14.0, 20.7, 21.0, 22.5, 25.0, 29.0, 30.7,
31.6, 65.1, 71.6, 170.6, 170.8; ESI-MS: m/z=253 (M+Na)+;
ESI-HR-MS: m/z=253.14177 (M+Na)+, calcd. for
C12H22NaO4: 253.14158.
E/Z-1,2-Diphenylethane-1,2-diyl diacetate (2j):[25] Mixture
of diastereomers (syn/anti=7:1); white solid; yield: 81%
(241 mg); FT-IR (KBr): n=702, 933, 1037, 1226, 1375, 1454,
1-(4-Chlorophenyl)ethane-1,2-diyl
diacetate
(2d):[43]
Yellow liquid; yield: 72% (184 mg); FT-IR (neat): n=826,
1737, 2854, 2926, 3033 cmÀ1 1H NMR (300 MHz, CDCl3;
;
1014, 1048, 1223, 1370, 1493, 1744, 2852, 2925 cmÀ1
;
normalized values, integral values 2H=1H): d=2.01 (s,
3.1H=1.55H), 2.08 (s, 21.1H=10.55H), 6.05 (s, 7H=
3.5H), 6.08 (s, 1H=0.5H), 7.13–7.16 (m, 14.1H=7.05H),
7.19–7.23 (m, 22.9H=11.45H), 7.27–7.29 (m, 3.1H=
1.55H); 13C NMR (75 MHz, CDCl3): d=20.9, 21.0, 76.4,
77.0, 127.47, 127.52, 128.0, 128.1, 128.3, 136.0, 136.1, 169.5,
169.7 (one signal is overlapping); ESI-MS: m/z=321 (M+
Na)+; ESI-HR-MS: m/z=321.11091 (M+Na)+, calcd. for
C18H18NaO4: 321.11028.
1H NMR (300 MHz, CDCl3): d=2.05 (s, 3H), 2.11 (s, 3H),
4.21–4.37 (m, 2H), 5.97 (dd, 1H, J=4.3, 7.3 Hz), 7.27–7.39
(m, 4H); 13C NMR (75 MHz, CDCl3): d=20.7, 21.0, 65.7,
72.6, 128.1, 128.8, 134.4, 135.0, 169.9, 170.5; ESI-MS: m/z=
279 (M+Na)+; ESI-HR-MS: m/z=279.04019 (M+Na)+,
calcd. for C12H13ClNaO4: 279.04001.
1-(4-Bromophenyl)ethane-1,2-diyl
Yellow liquid; yield: 85% (256 mg); FT-IR (neat): n=822,
1011, 1050, 1222, 1371, 1490, 1746, 2854, 2926 cmÀ1
diacetate
(2e):[44]
;
E/Z-2,3-Dihydro-1H-indene-1,2-diyl diacetate (2k):[25]
Mixture of diastereomers (syn/anti=14.3:1); colourless
liquid; yield: 88% (206 mg); FT-IR (neat): n=756, 963,
1022, 1064, 1247, 1373, 1434, 1462, 1742, 2854, 2925,
1H NMR (300 MHz, CDCl3): d=2.05 (s, 3H), 2.11 (s, 3H),
4.26 (dd, 1H, J=7.7, 11.9 Hz), 4.31 (dd, 1H, J=3.9,
11.9 Hz), 5.95 (dd, 1H, J=3.9, 7.7 Hz), 7.24 (d, 2H, J=
8.3 Hz), 7.50 (d, 2H, J=8.3 Hz); 13C NMR (75 MHz,
CDCl3): d=20.7, 21.0, 65.6, 72.6, 122.6, 128.4, 131.8, 135.5,
169.9, 170.5; ESI-MS: m/z=323 (M+Na)+; ESI-HR-MS:
m/z=322.98900 (M+Na)+, calcd. for C12H13BrNaO4:
322.98949.
3030 cmÀ1 1H NMR (300 MHz, CDCl3; normalized values,
;
integral values 10H=1H) d=2.07 (s, 29.8H=2.98H), 2.09
(s, 31.5H=3.15H), 3.13 (dd, 11.4H=1.14H, J=5.7,
16.0 Hz), 3.24 (dd, 11.5H=1.15H, J=6.7, 16.0 Hz), 5.52–
5.57 (m, 10.5H=1.05H), 6.22 (d, 10H=1H, J=5.3 Hz),
7.26–7.41 (m, 42.7H=4.27H); 13C NMR (75 MHz, CDCl3):
d=20.80, 20.84, 35.8, 73.2, 75.0, 124.9, 125.7, 127.3, 129.5,
138.0, 140.1, 170.42, 170.44; ESI-MS: m/z=257 (M+Na)+;
ESI-HR-MS: m/z=257.07809 (M+Na)+, calcd. for
C13H14NaO4: 257.07898.
1-(Naphthalen-2-yl)ethane-1,2-diyl
Yellow liquid; yield: 85% (231 mg); FT-IR (neat): n=750,
820, 1047, 1222, 1369, 1743, 2852, 2927 cmÀ1 1H NMR
diacetate
(2f):[25]
;
(300 MHz, CDCl3): d=2.06 (s, 3H), 2.15 (s, 3H), 4.37–4.44
(m, 2H), 6.18 (dd, 1H, J=4.4, 7.6 Hz), 7.46–7.51 (m, 3H),
7.82–7.87 (m, 4H); 13C NMR (75 MHz, CDCl3): d=20.7,
21.1, 66.0, 73.4, 124.1, 126.1, 126.4, 127.7, 128.0, 128.5, 133.0,
133.2, 133.8, 170.1, 170.6; ESI-MS: m/z=295 (M+Na)+;
ESI-HR-MS: m/z=295.09343 (M+Na)+, calcd. for
C16H16O4Na: 295.09408.
E/Z-1,2,3,4-Tetrahydronaphthalene-1,2-diyl
diacetate
(2l):[25] Mixture of diastereomers (syn/anti=1.5:1); colour-
less liquid; yield: 79% (196 mg); FT-IR (neat): n=748, 967,
1
1042, 1245, 1369, 1740, 2932, 3025 cmÀ1; H NMR (300 MHz,
CDCl3): d=1.92–2.02 (m, 2H), 2.04 (s, 3H), 2.05 (s, 3H),
2.09 (s, 3H), 2.11(s, 3H), 2.14–2.22 (m, 2H), 2.87–3.07 (m,
4H), 5.15–5.29 (m, 2H), 6.07 (d, 1H, J=5.8 Hz), 6.18 (d,
1H, J=3.2 Hz), 7.13–7.30 (m, 8H); 13C NMR (75 MHz,
CDCl3): d=21.05, 21.05, 23.3, 24.9, 25.6, 27.0, 69.2, 70.0,
71.0, 71.4, 126.38, 126.42, 128.2, 128.5, 128.6, 128.7, 129.0,
129.9, 132.6, 136.3, 136.5, 170.2, 170.3, 170.5 (some signals
are overlapping); ESI-MS: m/z=271 (M+Na)+; ESI-HR-
MS: m/z=271.09469 (M+Na)+, calcd. for C14H16NaO4:
271.09463.
2-Phenylpropane-1,2-diyl diacetate (2g):[21] Yellow liquid;
yield: 72% (170 mg); FT-IR (neat): n=700, 765, 1046, 1130,
1
1235, 1370, 1448, 1743, 2854, 2927 cmÀ1; H NMR (300 MHz,
CDCl3): d=1.89 (s, 3H), 2.05 (s, 3H), 2.08 (s, 3H), 4.30 (d,
1H, J=11.5 Hz), 4.39 (d, 1H, J=11.5 Hz), 7.26–7.38 (m,
5H); 13C NMR (75 MHz, CDCl3): d=20.7, 21.8, 22.0, 69.8,
81.5, 124.8, 127.6, 128.3, 141.1, 169.3, 170.4; ESI-MS: m/z=
259 (M+Na)+; ESI-HR-MS: m/z=259.09367 (M+Na)+,
calcd. for C13H16O4Na: 259.09408.
1-(4-Acetoxyphenyl)ethane-1,2-diyl diacetate (2h): Yellow
liquid; yield: 65% (182 mg); FT-IR (neat): n=850, 911,
cis-Acetic acid 2-hydroxy-2-phenylcyclohexyl ester
(2m):[44] (syn/anti= >99:1); white solid; yield: 92%
(215 mg); FT-IR (KBr): n=699, 757, 994, 1034, 1079, 1253,
1015, 1047, 1169, 1221, 1371, 1509, 1745, 2956 cmÀ1
;
1H NMR (300 MHz, CDCl3): d=2.06 (s, 3H), 2.11 (s, 3H),
2.30 (s, 3H), 4.27 (dd, 1H, J1 =8.0, J2 =11.9 Hz), 4.33 (dd,
1H, J1 =3.8, J2 =11.9 Hz), 6.02 (dd, 1H, J=3.8, 8.0 Hz), 7.10
(d, 2H, J=8.5 Hz), 7.39 (d, 2H, J=8.5 Hz); 13C NMR
(75 MHz, CDCl3): d=20.7, 21.0, 21.1, 65.9, 72.6, 121.8,
127.9, 134.0, 150.7, 169.3, 169.9, 170.6; ESI-MS: m/z=303
(M+Na)+; ESI-HR-MS: m/z=303.08323 (M+Na)+, calcd.
for C14H16O6Na: 303.08391.
1376, 1718, 2857, 2940, 3026, 3532 cmÀ1; H NMR (300 MHz,
1
CDCl3): d=1.45–1.58 (m, 2H), 1.65–1.78 (m, 2H), 1.80 (s,
3H), 1.83–1.93 (m, 4H), 2.27 (br s, 1H), 5.29 (dd, 1H, J=
5.0, 10.6 Hz), 7.21–7.26 (m, 1H), 7.30–7.35 (m, 2H), 7.43–
7.47 (m, 2H); 13C NMR (75 MHz, CDCl3): d=20.8, 21.0,
24.1, 27.1, 39.7, 75.2, 76.2, 124.6, 126.9, 128.2, 145.9, 169.7;
ESI-MS: m/z=257 (M+Na)+; ESI-HR-MS: m/z=
257.11598 (M+Na)+, calcd. for C14H18NaO3: 257.11536.
2-Oxo-2-phenylethyl acetate (4a):[45] yellow liquid; yield:
81% (144 mg); FT-IR (KBr): n=562, 632, 686, 754, 968,
1080, 1227, 1373, 1426, 1600, 1699, 1742, 2939, 3066,
Octane-1,2-diyl diacetate (2i):[21] Colourless liquid; yield:
88% (202 mg); FT-IR (neat): n=1046, 1226, 1371, 1744,
2858, 2929 cmÀ1 1H NMR (300 MHz, CDCl3): d=0.88 (t,
;
Adv. Synth. Catal. 2015, 357, 3587 – 3596
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3593