NMR (101 MHz, DMSO-d6) δ 190.6, 168.6, 145.5, 139.4, 137.3,
1H NMR (400 MHz, CDCl3) δ 8.16 (br s, 1H), 7.23 (d, 1H, J =
7.7 Hz), 7.22 (t, 1H, J = 7.7 Hz), 7.04 (t, 1H, J = 7.7 Hz), 6.88
(1H, d, J = 7.7 Hz), 3.46 (1H, t, J = 5.8 Hz), 2.04 (m, 2H), 0.93
(t, 3H, J = 7.5 Hz). 13C NMR (101 MHz, CDCl3) δ 180.1, 141.6,
129.5, 127.8, 124.1, 122.2, 109.5, 47.0, 23.5, 9.9
ACCEPTED MANUSCRIPT
136.2, 133.6, 131.0, 129.7, 127.3, 125.8, 122.2, 120.4, 110.9.
max(ATR) 3146, 3085, 1715, 1495, 1327. HRMS (EI): calculated
ν
for C16H10ClNO2: 283.0400; found 283.0404.
4.5.11. (Z)-3-(2-(4-methoxyphenyl)-2-
oxoethylidene)indolin-2-one 11.
4.7.3. 3-benzylindolin-2-one 17
Brown solid. m.p. 197°C 1H NMR (400 MHz, DMSO-d6) δ
10.76 (s, 1H), 8.06 (d, J = 8.9 Hz, 2H), 7.94 (d, J = 7.7 Hz, 1H),
7.69 (s, 1H), 7.33 (td, J = 7.7, 1.3 Hz, 1H), 7.13 (d, J = 8.9 Hz,
2H), 6.94 (td, J = 7.7, 1.3 Hz, 1H), 6.88 (dt, J = 7.8, 0.8 Hz, 1H),
3.88 (s, 3H). 13C NMR (101 MHz, DMSO-d6) δ 190.2, 168.7,
164.4, 145.1, 136.0, 133.0, 131.6, 130.4, 127.1, 127.0, 122.1,
120.5, 114.9, 110.8, 56.2. νmax(ATR) 3147, 1706, 1603, 1457,
1010. HRMS (EI): calculated for C17H13NO3: 279.0895; found
279.0893.
1H NMR (400 MHz, CDCl3) δ 9.32 (1H, br s), 7.29‐7.15 (6H,
m), 7.03 (1H, td, J = 7.5, 1.0 Hz), 6.92‐6.86 (2H, m); 6.75 (1H, d,
J = 7.4 Hz), 3.77 (1H, dd, J = 9.3, 4.5 Hz), 3.52 (1H, dd, J =
13.7, 4.6 Hz), 2.95 (1H, dd, J = 13.7, 9.3 Hz); 13C NMR (101
MHz, CDCl3) δ 180.1, 141.5, 137.8, 129.4, 129.0, 128.3, 127.9,
126.6, 124.7, 121.9, 109.8, 47.6, 36.6.
4.7.4. methyl 2-(2-oxoindolin-3-yl)acetate 18
1H NMR (400 MHz, CDCl3) δ 8.88 (br s, 1H), 7.24-7.20 (m,
2H), 7.01 (d, J = 7.6 Hz, 1H), 6.91 (d, J = 8.0 Hz, 1H), 3.82 (dd,
J = 4.8, 8.0 Hz, 1H), 3.70 (s, 3H), 3.09 (dd, J = 4.4, 16.8 Hz, 1H),
2.84 (dd, J = 8.0, 16.8 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ
179.2, 171.6, 141.5, 128.6, 128.3, 124.1, 122.5, 109.9, 52.1, 42.3,
34.5
4.5.12. (Z)-3-(2-(furan-2-yl)-2-
oxoethylidene)indolin-2-one 12.
Red solid. m.p. 188°C 1H NMR (400 MHz, DMSO-d6) δ
10.80 (s, 1H), 8.48 (d, J = 7.8 Hz, 1H), 8.14 (d, J = 1.0 Hz, 1H),
7.71 (dd, J = 3.7, 1.0 Hz, 1H), 7.59 (s, 1H), 7.39 (td, J = 7.7, 1.0
Hz, 1H), 7.03 (dd, J = 7.6, 1.1 Hz, 1H), 6.89 (d, J = 8.1 Hz, 1H),
6.83 (dd, J = 3.7, 1.7 Hz, 1H). 13C NMR (101 MHz, DMSO-d6) δ
177.2, 168.7, 153.8, 149.6, 145.8, 133.2, 128.6, 128.0, 126.0,
124.2, 122.3, 120.6, 113.9, 110.8. νmax(ATR) 3186, 2921, 1706,
1458, 1328. HRMS (EI): calculated for C14H9NO3: 239.0582;
found 239.0581.
4.7.5. 2-(2-oxoindolin-3-yl)acetonitrile 19
1H NMR (400 MHz, DMSO-d6) δ 10.62 (1H, s,), 7.39 (1H, d,
J=7.4 Hz), 7.24 (1H, t, J=7.7 Hz), 7.01 (1H, t, J=7.5 Hz), 6.88
(1H, d, J=7.7 Hz), 3.82 (1H, t, J=5.9 Hz), 3.20 (1H, dd, J=17.2,
5.8 Hz), 3.06 (1H, dd, J=17.2, 5.9 Hz). 13C NMR (101 MHz,
DMSO-d6) δ 176.4, 142.8, 128.6, 127.1, 124.2, 121.6, 118.2,
109.6, 41.3, 17.6.
4.5.13. ethyl-2-cyano-2-(2-oxoindolin-3-
ylidene)acetate 13
4.7.6. methyl 2-(5-methoxy-2-oxoindolin-3-
1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 8.0 Hz, 1H), 7.56
(s, 1H), 7.13 (t, J = 7.7 Hz, 1H), 6.71 (t, J = 7.8 Hz, 1H), 6.61 (d,
J = 8.3 Hz, 1H), 4.21 (q, J = 7.2 Hz, 2H), 1.19 (t, J = 7.1 Hz,
3H). 13C NMR (101 MHz, CDCl3) δ 165.2, 164.5, 163.8, 135.9,
127.9, 126.8, 126.4, 124.0, 120.3, 117.2, 106.3, 59.1, 13.7.
yl)acetate 21
1
Orange solid. m.p. decompose. H NMR (400 MHz, CD3CN)
δ 8.31 (s, 1H), 6.90 – 6.70 (m, 3H), 3.76 (s, 3H), 3.70 – 3.65 (m,
1H), 3.64 (s, 3H), 3.00 (dd, J = 16.8, 5.3 Hz, 1H), 2.86 (dd, J =
17.0, 6.9 Hz, 1H). 13C NMR (101 MHz, CD3CN) δ 171.5, 166.6,
155.9, 139.4, 138.9, 123.1, 121.7, 119.2, 114.6, 111.3, 56.0, 52.5.
νmax(ATR) 3263, 2924, 1711, 1487, 1203. HRMS (EI): calculated
for C12H13NO4: 235.0845; found 235.0841.
4.5.14. 2-(2-oxoindolin-3-ylidene)malononitrile14
1H NMR (400 MHz, DMSO-d6) δ 11.21 (s, 1H), 7.89 (d, J =
8.0 Hz, 1H), 7.57 (dd, J = 8.0, 7.6 Hz, 1H), 7.14 (dd, J = 8.0, 7.6
Hz, 1H), 6.93 (d, J = 8.0 Hz, 1H). 13C NMR (101 MHz, DMSO-
d6) δ 164.7, 151.5, 147.4, 138.7, 126.7, 123.8, 119.6, 114.0,
112.5, 112.4, 81.5.
4.7.7. 3-(2-hydroxypropyl)indolin-2-one 24. mixture
of two diastereoisomers.
Yellow solid. m.p. 84°C (decompose) 1H NMR (400 MHz,
CDCl3) δ 9.01 (s, 0.5H, diast A), 8.80 (s, 0.5H, diast B), 7.25 –
7.13 (m, 2H), 7.09 – 6.98 (m, 1H), 6.93 – 6.84 (m, 1H), 4.24 (td,
J = 6.4, 3.0 Hz, 0.5H, diast A), 4.17 – 4.08 (m, 0.5H, diast B),
3.73 – 3.60 (m, 1H), 2.89 (d, J = 6.3 Hz, 1H), 2.16 (ddd, J = 14.0,
9.1, 4.7 Hz, 0.5H, diast A), 2.04 – 1.82 (m, 1.5H), 1.30 (d, J = 6.2
Hz, 1.5H, diast A), 1.27 (d, J = 6.3 Hz, 1.5H, diast B). 13C NMR
(101 MHz, Chloroform-d) δ 181.7 and 181.6, 141.3 and 141.1,
129.4 and 129.3, 127.1 and 126.8, 123.9 and 123.8, 122.7 and
122.5, 110.1 and 109.9, 64.4 and 64.2, 44.7 and 44.2, 41.1 and
40.0, 23.6 and 23.3. νmax(ATR) 3437, 2925, 2987, 1470, 1137.
HRMS (EI): calculated for C11H13NO2: 191.0946; found
191.0944.
4.6. General procedure for the baker’s yeast reduction of olefins
To a mixture of commercial fresh or freeze-dried baker’s yeast
(Sigma) (7.5 g) in tap water (50 mL) at 40°C, D-glucose (0.75g,
4.17 mmol) was added. The substrate (100 mg) was added and
the flask was placed for 2 d in a termo-shaker. The mixture was
then filtered on a celite pad and washed twice with water (50 mL)
and once with EtOAc (50 mL). The aqueous was extracted with
EtOAc (3 × 50 mL). The combined organic layers were dried
(Na2SO4) and the solvent was removed under reduced pressure.
The crude residue was purified by silica gel column
chromatography eluting with 4:6 EtOAc/hexane to give the
product.
4.7.8. 3-(2-hydroxy-2-phenylethyl)indolin-2-one 25.
4.7. Spectroscopic data for compounds 15-17,48 and 18, 1949
were in agreement with literature values.
Yellow solid. m.p. 104°C mixture of two diastereoisomers.
1H NMR (400 MHz, CDCl3) δ 9.03 (s, 0.5H, diast A), 8.90 (s,
0.5H, diast B), 7.38 – 6.98 (m, 8H), 6.91 – 6.80 (m, 1H), 5.12 –
5.03 (m, 1H), 4.74 (s, 0.5H, diast A), 4.17 (s, 0.5H, diast B), 3.69
(t, J = 7.0 Hz, 0.5H, diast A), 3.59 (dd, J = 9.3, 3.9 Hz, 0.5H,
diast B), 2.40 (ddd, J = 14.6, 8.1, 4.0 Hz, 0.5H, diast A), 2.27 –
2.10 (m, 1.5H). 13C NMR (101 MHz, CDCl3) δ 181.7 and 181.6,
142.8 and 142.6, 141.3 and 141.1, 133.2 and 133.0, 129.4 and
129.3, 128.8 - 128.6 (2C), 128.3 and 128.1, 127.3 and 127.0
(2C), 124.0 and 123.8, 122.9 and 122.7, 110.2 and 110.1, 72.8
and 70.5, 45.3 and 43.0, 40.3 and 39.0. νmax(ATR) 3250, 1698,
4.7.1. 3-methylindolin-2-one 15
1H NMR (400 MHz, CDCl3) δ 9.23 (1H, br s), 7.21 (2H, td, J
= 7.4, 0.8 Hz), 7.03 (1H, td, J = 7.5, 1.0 Hz), 6.93 (1H, d, J = 7.5
Hz), 3.47 (1H, q, J = 7.7 Hz), 1.51 (3H, d, J = 7.7 Hz). 13C NMR
(101 MHz, CDCl3) δ 181.4, 141.2, 131.2, 127.9, 123.8, 122.3,
109.7, 41.0, 15.2.
4.7.2. 3-ethylindolin-2-one 16