Job/Unit: O31366
/KAP1
Date: 14-11-13 19:05:51
Pages: 13
Enantioselective Reactions of Homoenolates
was purified by flash chromatography on silica gel with MeOH/
CH2Cl2 or AcOEt/PE as eluent to give the pure product.
55.7 (CH3), 55.6 (CH3), 50.8 (CH2), 45.1 (CH2), 38.7 (CH2), 28.2
(CH), 21.1 (CH3), 19.9 (2 CH3), 19.0 (2 CH3) ppm. 19F NMR
(376.5 MHz, CDCl3): δ = –71.0 (d, JF,P = 713.8 Hz) ppm. 31P NMR
(162 MHz, CDCl3): δ = –144.1 (sept, JP,F = 713.8 Hz) ppm. HRMS
Compound 12a: Pale-yellow solid (1.19 g, 75%); Rf = 0.38 (CH2Cl2/
MeOH, 95:5); m.p. 96–98 °C (amorphous); [α]2D5 = –9.0 (c = 1.0,
+
(ESI+): calcd. for C26H37N4O3 453.2860 [M]+; found 453.2860.
1
CHCl3). H NMR (400 MHz, CDCl3): δ = 7.89 (s, 2 H), 7.76 (s, 1
H), 7.56 (s, NH), 7.46 (s, 1 H), 6.84 (s, 2 H), 5.84 (br. s, 1 H, NH),
4.68–4.36 (m, 1 H), 4.31–3.95 (m, 3 H), 3.83–3.51 (m, 2 H), 3.43
Compound 12e: Pale-yellow solid (0.50 g, 72%); Rf = 0.40 (CH2Cl2/
MeOH, 95:5); m.p. 90–92 °C (amorphous); [α]2D5 = +11 (c = 1.0,
(d, J = 13.8 Hz, 1 H), 2.23 (s, 3 H), 2.11 (br. s, 3 H), 2.03–1.85 (m, CHCl3). 1H NMR (400 MHz, CDCl3): δ = 7.99 (dd, J = 7.9,
4 H), 1.06 (d, J = 6.7 Hz, 3 H), 1.03 (d, J = 6.7 Hz, 3 H) ppm. 13C
1.5 Hz, 1 H), 7.79 (s, 1 H), 7.39 (s, 1 H, NH), 6.93 (td, J = 7.7,
1.6 Hz, 1 H), 6.84 (ddd, J = 14.0, 7.8, 1.3 Hz, 4 H), 5.81 (t, J =
NMR (100 MHz, CDCl3): δ = 158.05 (CH), 155.54 (C), 140.9 (C),
2
140.8 (C), 134.8 (2 C), 132.1 (q, JC,F = 33.2 Hz, 2 C), 130.1 (2 4.1 Hz, 1 H, NH), 4.63–4.53 (m, 1 H), 4.19–3.98 (m, 4 H), 3.81 (s,
1
CH), 130.0 (C), 129.9 (2 CH), 123.2 (q, JC,F = 272.8 Hz, 2 C),
118.33 (CH), 115.62 (CH), 66.57 (CH), 50.79 (CH2), 45.66 (CH2),
38.70 (CH2), 28.25 (CH), 20.99 (CH3), 19.72 (2 CH3), 19.03 (2
CH3) ppm. 19F NMR (376.5 MHz, CDCl3): δ = –63.0 (s), –71.0 (d,
3 H), 3.72–3.61 (m, 2 H), 3.33 (dt, J = 15.8, 6.1 Hz, 1 H), 2.23 (s,
3 H), 2.14 (s, 3 H), 1.90 (s, 3 H), 1.33 (td, J = 7.1, 0.9 Hz, 1 H),
1.04 (d, J = 6.6 Hz, 3 H), 1.01 (d, J = 6.6 Hz, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 156.4 (CH), 156.0 (C), 148.2 (C), 140.6
JF,P = 713.8 Hz) ppm. 31P NMR (162 MHz, CDCl3): δ = –144.1 (C), 135.7 (C), 134.9 (C), 130.1 (C), 130.0 (CH), 129.9 (CH), 128.6
(sept, JP,F
=
713.8 Hz) ppm. HRMS (ESI+): calcd. for
(C), 122.3 (CH), 120.7 (CH), 116.7 (CH), 110.2 (CH), 66.4 (CH),
55.7 (CH3), 50.8 (CH2), 45.1 (CH2), 38.6 (CH2), 28.2 (CH), 21.0
(CH3), 19.9 (2 CH3), 19.1 (2 CH3) ppm. 19F NMR (376.5 MHz,
CDCl3): δ = –71.0 (d, JF,P = 713.8 Hz) ppm. 31P NMR (162 MHz,
CDCl3): δ = –144.1 (sept, JP,F = 713.8 Hz) ppm. HRMS (ESI+):
C26H31N4OF6 529.2397 [M]+; found 529.2397.
+
Compound 12b: Pale-yellow solid (0.54 g, 85%); Rf = 0.45 (CH2Cl2/
MeOH, 95:5); m.p. 87–89 °C (amorphous); [α]2D5 Ͻ +2.0 (c = 1.0,
CHCl3). 1H NMR (400 MHz, CDCl3): δ = 7.74 (s, 1 H), 7.33 (d, J
= 7.6 Hz, 2 H), 7.21 (t, J = 7.9 Hz, 2 H), 7.13 (s, 1 H, NH), 6.96
+
calcd. for C25H35N4O2 423.2755 [M]+; found 423.2751.
(t, J = 7.4 Hz, 1 H), 6.83 (s, 2 H), 5.69 (dd, J = 8.0, 4.1 Hz, 1 H, Compound 12f: Light-brown solid (0.40 g, 59%); Rf = 0.40
NH), 4.59–4.47 (m, 1 H), 4.18–3.95 (m, 3 H), 3.73–3.49 (m, 2 H),
3.37–3.28 (m, 1 H), 2.22 (s, 3 H), 2.12 (br. s, 3 H), 1.91 (br. s, 3 H),
1.33 (td, J = 7.1, 1 H, 0.8 Hz), 1.03 (d, J = 6.6 Hz, 3 H), 0.99 (d,
J = 6.6 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.1
(CH), 155.2 (C), 140.5 (C), 139.0 (2 C), 134.8 (C), 130.0 (C), 129.9
(CH), 129.8 (CH), 128.8 (2 CH), 122.6 (CH), 119.0 (2 CH), 66.4
(CH2Cl2/MeOH, 95:5); m.p. 79–81 °C (amorphous); [α]2D5 = +32 (c
= 1.0, CHCl3). 1H NMR (400 MHz, CDCl3): δ = 7.99 (t, J =
6.4 Hz, 1 H), 7.93 (s, 1 H), 7.80 (dd, J = 8.5, 3.1 Hz, 2 H), 7.56 (t,
J = 8.1 Hz, 2 H), 7.45 (ddd, J = 9.6, 2.8, 0.9 Hz, 2 H), 7.39 (t, J =
7.9 Hz, 1 H), 6.84 (s, 1 H), 6.68 (s, 1 H), 6.25 (d, J = 6.4 Hz, 1 H,
NH), 4.64–4.53 (m, 1 H), 4.23–4.13 (m, 1 H), 4.01–3.91 (m, 2 H),
(CH), 50.7 (CH2), 45.2 (CH2), 36.5 (CH2), 26.1 (CH), 21.0 (2 CH3), 3.71 (quint, J = 11.0 Hz, 2 H), 3.42–3.30 (m, 1 H), 2.21 (s, 3 H),
19.7 (CH3), 17.0 (2 CH3) ppm. 19F NMR (376.5 MHz, CDCl3): δ
= –71.0 (d, JF,P = 713.8 Hz) ppm. 31P NMR (162 MHz, CDCl3): δ
= –144.1 (sept, JP,F = 713.8 Hz) ppm. HRMS (ESI+): calcd. for
C24H33N4O+ 393.2649 [M]+; found 393.2647.
2.11 (br. s, 3 H), 1.98–1.82 (m, 1 H), 1.81 (br. s, 3 H), 1.05 (d, J =
6.6 Hz, 3 H), 1.01 (d, J = 6.6 Hz, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 158.2 (CH), 156.9 (C), 140.4 (C), 134.0 (2 C), 133.7
(C), 130.0 (2 C), 129.9 (CH), 128.4 (CH), 127.1 (C), 126.2 (CH),
126.0 (CH), 125.6 (2 CH), 124.3 (CH), 121.2 (CH), 119.2 (CH),
66.2 (CH), 50.7 (CH2), 45.3 (CH2), 38.8 (CH2), 28.2 (CH), 21.0 (2
CH3), 19.7 (2 CH3), 19.0 (CH3) ppm. 19F NMR (376.5 MHz,
CDCl3): δ = –71.0 (d, JF,P = 713.8 Hz) ppm. 31P NMR (162 MHz,
CDCl3): δ = –144.1 (sept, JP,F = 713.8 Hz) ppm. HRMS (ESI+):
calcd. for C28H35N4O+ 443.2805 [M]+; found 443.2804.
Compound 12c: Yellow solid (0.61 g, 79%); Rf = 0.36 (CH2Cl2/
MeOH, 95:5); m.p. 82–84 °C (amorphous); [α]2D5 = +4.1 (c = 1.0,
CHCl3). 1H NMR (400 MHz, CDCl3): δ = 7.82 (s, 1 H), 7.24 (d, J
= 9.0 Hz, 2 H), 6.99 (s, 1 H, NH), 6.85 (d, J = 5.8 Hz, 2 H), 6.78
(d, J = 9.0 Hz, 2 H), 5.66 (d, J = 7.6 Hz, 1 H, NH), 4.60–4.50 (m,
1 H), 4.20–3.91 (m, 3 H), 3.76 (s, 3 H), 3.69–3.55 (m, 2 H), 3.34
(td, J = 11.4, 3.4 Hz, 1 H), 2.24 (s, 3 H), 2.14 (s, 3 H), 1.98 (br. s,
Compound 12g: Pale-yellow solid (0.21 g, 73%); Rf = 0.50 (CH2Cl2/
3 H), 1.93–1.87 (m, 1 H), 1.05 (d, J = 6.6 Hz, 3 H), 1.01 (d, J = MeOH, 95:5); m.p. 119–121 °C (amorphous); [α]2D5 = +74 (c = 1.0,
6.6 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.4 (CH),
156.5 (C), 155.6 (C), 140.7 (C), 135.7 (C), 132.2 (C), 130.1 (2 C),
130.0 (CH), 129.9 (CH), 121.2 (2 CH), 114.0 (2 CH), 66.6 (CH),
CHCl3). H NMR (400 MHz, CDCl3): δ = 7.89 (s, 1 H), 6.92 (s, 2
H), 6.80 (s, 2 H), 4.48 (s, 1 H), 4.21 (dd, J = 14.3, 6.3 Hz, 1 H),
4.07–3.90 (m, 2 H), 3.69 (td, J = 10.4, 3.0 Hz, 1 H), 3.5 (d, J =
1
55.6 (CH3), 50.6 (CH2), 45.3 (CH2), 38.7 (CH2), 28.3 (CH), 21.1 7.5 Hz, 1 H), 3.31 (d, J = 13.6 Hz, 1 H), 2.29 (s, 3 H), 2.21 (s, 3
(CH3), 19.9 (2 CH3), 19.1 (2 CH3) ppm. 19F NMR (376.5 MHz,
CDCl3): δ = –71.0 (d, JF,P = 713.8 Hz) ppm. 31P NMR (162 MHz,
CDCl3): δ = –144.1 (sept, JP,F = 713.8 Hz) ppm. HRMS (ESI+):
H), 2.17 (s, 6 H), 2.07 (s, 6 H), 1.94–1.85 (m, 1 H), 1.02 (t, J =
6.4 Hz, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.4 (CH),
157.4 (C), 140.6 (4 C), 136.0 (C), 130.3 (2 C), 130.2 (4 CH), 129.0
(C), 66.1 (CH), 50.7 (CH2), 45.4 (CH2), 39.2 (CH2), 28.4 (CH),
21.1 (CH3), 21.0 (CH3), 19.7 (CH3), 19.1 (CH3), 18.3 (2 CH3), 17.6
+
calcd. for C25H35N4O2 423.2755 [M]+; found 423.2752.
Compound 12d: Yellow solid (0.48 g, 68%); Rf = 0.40 (CH2Cl2/
MeOH, 95:5); m.p. 85–88 °C (amorphous); [α]2D5 = +19 (c = 1.0,
CHCl3). 1H NMR (400 MHz, CDCl3): δ = 7.83 (s, 1 H), 7.74 (d, J
= 8.7 Hz, 2 H), 7.02 (s, 1 H, NH), 6.84 (d, J = 13.0 Hz, 2 H), 6.42
(d, J = 2.6 Hz, 1 H), 6.38 (dd, J = 8.8, 2.6 Hz, 1 H), 5.71 (d, J =
2.9 Hz, 1 H, NH), 4.65–4.50 (m, 1 H), 4.20–3.93 (m, 3 H), 3.76 (s,
(2 CH3) ppm. 19F NMR (376.5 MHz, CDCl3): δ = –71.0 (d, JF,P
=
713.8 Hz) ppm. 31P NMR (162 MHz, CDCl3): δ = –144.1 (sept,
JP,F = 713.8 Hz) ppm. HRMS (ESI+): calcd. for C27H39N4O+
435.3118 [M]+; found. 435.3116.
Compound 12h: Light-brown solid (0.32 g, 74%); Rf = 0.40
3 H), 3.74 (s, 3 H), 3.67–3.59 (m, 2 H), 3.34–3.30 (m, 1 H), 2.23 (s, (CH2Cl2/MeOH, 95:5); m.p. 99–101 °C (amorphous); [α]2D5 Ͻ +2.0
1
3 H), 2.14 (s, 3 H), 1.97 (br. s, 3 H), 1.33 (t, J = 7.1 Hz, 1 H), 1.03
(d, J = 6.7 Hz, 3 H), 1.00 (d, J = 6.6 Hz, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 158.4 (CH), 156.4 (C), 156.0 (C), 150.2
(C), 140.5 (C), 135.8 (C), 135.0 (C), 130.2 (C), 130.0 (CH), 129.9
(c = 1.0, CHCl3). H NMR (400 MHz, CDCl3): δ = 7.89 (s, 2 H),
7.80 (s, 1 H), 7.53 (s, 1 H, NH), 7.47 (s, 1 H), 6.84 (s, 2 H), 5.90
(dd, J = 8.1, 4.5 Hz, 1 H, NH), 4.65–4.43 (m, 1 H), 4.29–3.97 (m,
4 H), 3.74–3.57 (m, 1 H), 3.24 (dt, J = 14.8, 3.7 Hz, 1 H), 2.23 (s,
(CH), 121.8 (CH), 120.7 (CH), 103.9 (CH), 98.7 (CH), 66.3 (CH), 3 H), 2.13 (br. s, 3 H), 1.88 (br. s, 3 H),1.69–1.52 (m, 2 H), 1.50–
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