ACCEPTED MANUSCRIPT
added. The reaction mixture was stirred for 3 h and filtered. The precipitate was washed with CH Cl . The filtrate was
2
2
concentrated under reduced pressure and the crude product was purified by flash chromatography.
4
.2.7.1. 3-(9H-Fluoren-9-yl)-1-(phenylmethyl)- 2,5-pyrrolidinedione (8a). The desired product was synthesized according
to Method A and was purified by flash chromatography (PE/EtOAc – 8:2) to give 8a as white crystals (49 mg, 69%). Mp:
-
1
1
5
159 °C. IR (ν, cm ) 1769, 1701, 1491, 1401; H NMR (300 MHz, CDCl ): δ = 1.37 (dd, J = 4.8 Hz, J = 18.6 Hz, 1H), 2.22
3
(
dd, J = 9.0 Hz, J = 18.6 Hz, 1H), 3.67 (ddd, J = 3.6 Hz, J = 4.8 Hz, J = 9 Hz, 1H), 4.64–4.81 (m, 3H), 6.70–6.86 (m, 2H),
1
3
7
1
.29–7.49 (m, 9H), 7.69–7.75 (m, 2H); C NMR (75 MHz, CDCl ): δ = 29.4, 43.6, 44.2, 46.8, 100.5, 107.2, 120.3, 123.8,
3
+
24.9, 127.6, 127.7, 128.1, 128.3, 137.7, 141.2, 141.3, 142.1, 144.2, 161.1, 176.0, 178.9; HRMS (TOF MS Cl ) m/z
+
(
M+H ) calculated for C H NO 354.1481; found 354.1487.
2
4
20
2
2
D
0
20
D
1
0
[α
] = +249.0 (c 0.3, CHCl
, ee 100 %), [
α
]
= −256.0 (c 0.25, CHCl , ee 98.5%). Chiral preparative SFC, Chiralpak OJ-
3
3
H 5µM (10˟ 250 mm) cellulose tris(4-methylbenzoate) with 25% CH CN, 40 °C, P=120 bar, flow rate 12 mL/min t d-
3
R
enantiomer 2.50 min, l-enantiomer 5.27 min.
4
.2.7.2. 1-(3,5-Dimethoxybenzyl)-3-(9H-fluoren-9-yl)-2,5-pyrrolidinedione (8b). The desired product was synthesized
1
5
according to Method B and was purified by flash chromatography (PE/CH Cl – 7:3) to give 8b as a lightly yellow solid
2
2
-
1
1
(
60 mg, 73%). Mp: 140 °C. IR (ν, cm ) 1773; 1699, 1607, 1597, 1432; H NMR (300 MHz, CDCl ): δ = 1.37 (dd, J = 4.8
3
Hz, J = 18.6 Hz, 1H), 2.22 (dd, J = 9.3 Hz, J = 18.6 Hz, 1H), 3.67 (ddd, J = 3.6 Hz, J = 4.8 Hz, J = 9.3 Hz, 1H), 3.79 (s,
H), 4.58 (d, J = 13.7 Hz, 1H), 4.67 (d, J = 3.6 Hz, 1H), 4.71 (d, J = 13.7 Hz, 1H), 6.45 (t, J = 2.4 Hz, 1H), 6.60 (d, J = 2.4
6
1
3
Hz, 2H), 6.79–6.83 (m, 1H), 6.92 (td, J = 1.2 Hz, J = 7.5 Hz, 1H), 7.28–7.49 (m, 4H), 7.72 (t, J = 7.8 Hz, 2H); C NMR
2
2
3
0
5
0
(75 MHz, CDCl ): δ = 29.4, 42.8, 42.9, 46.6, 55.5, 100.5, 107.2, 120.3, 123.8, 124.9, 127.6, 127.7, 128.1, 128.3, 137.7,
3
+
+
1
41.2, 141.3, 142.1, 144.2, 161.1, 176.0, 178.9. HRMS (TOF MS Cl ) m/z (M+H ) calculated for C H NO 414.1705;
26 24 4
found 414.1721.
4
.2.7.3. 3-(9H-Fluoren-9-yl)-1-nonyl-2,5-pyrrolidinedione (8c). The desired product was synthesized according to Method
-
1
A and was purified by flash chromatography (PE/EtOAc – 9:1) to give 8c as lightly yellow oil (37 mg, 71%). IR (ν, cm )
1
2
922, 2851, 1770, 1699, 1689, 1409; H NMR (300 MHz, CDCl ): δ = 0.86–0.95 (m, 5H), 1.24–1.41 (m, 9H), 1.50–1.65
3
(
m, 4H), 2.19 (dd, J = 9.1 Hz, J = 18.6 Hz, 1H), 3.55 (t, J = 7.5 Hz, 1H), 3.67 (ddd, J = 3.6 Hz, J = 5.1 Hz, J = 9.1 Hz, 1H),
1
3
4
1
.73 (d, J = 3.6 Hz, 1H), 7.17–7.24 (m, 2H), 7.31–7.51 (m, 4H), 7.76 (d, J = 7.5 Hz, 2H); C NMR (75 MHz, CDCl ): δ =
3
4.3, 22.8, 27.1, 27.9, 29.38, 29.41, 29.6, 32.0, 39.2, 43.2, 46.4, 120.4, 120.5, 123.9, 124.8, 127.6, 127.8, 128.1, 128.5,
+
141.3, 141.5, 142.3, 144.4, 176.5, 179.3; LRMS (DCI/NH ) [M+NH ] calculated for C H N O 407.5; found 407.2.
3
4
26 35
2
2
4
.2.7.4. 3-(9H-Fluoren-9-yl)-1-(2-oxo-2-phenylethyl)-2,5-pyrrolidinedione (8d). The product was synthesized according to
Method B and was purified by flash chromatography (PE/EtOAc – 7:3) to afford 8d as a white powder (72 mg, 94%). Mp:
-
1
1
1
86 °C. IR (ν, cm ) 2923, 1775, 1707, 1699, 1420; H NMR (300 MHz, CDCl ): δ = 1.57 (dd, J = 5.7 Hz, J = 18.6 Hz,
3
3
5
1H), 2.36 (dd, J = 9.3 Hz, J = 18.6 Hz, 1H), 3.90 (ddd, J = 3.6 Hz, J = 5.7 Hz, J = 9.3 Hz, 1H), 4.79 (d, J = 3.6 Hz, 1H),
1
3
4
4
.97 (d, J = 17.1 Hz, 1H), 5.05 (d, J = 17.1 Hz, 1H), 7.30–8.03 (m, 13H); C NMR (75 MHz, CDCl ): δ = 29.6, 43.6, 44.9,
3
6.2, 120.4, 123.9, 125.3, 127.8, 127.9, 128.2, 128.3, 128.5, 129.1, 134.2, 134.6, 141.4, 142.2, 144.4, 175.8, 178.7, 190.1;
+
+
HRMS (TOF MS Cl ) m/z (M+H ) calculated for C H NO 382.1443; found 382.1453.
2
5
20
3
-
10 -