Visible Light Driven Copper(I) Catalyzed Oxyamination of Electron Deficient Alkenes
Chin. J. Chem.
3-Morpholino-1-(naphthalen-1-yl)-1-oxopropan-2-yl benzoate
(3la) was obtained in 72% isolated yield (28.0 mg) as colorless
solid. 1H NMR (500 MHz, CDCl3) δ 8.48 (d, J = 8.4 Hz, 1H), 8.12 (d, J
= 7.4 Hz, 2H), 8.09 (d, J = 7.2 Hz, 1H), 8.00 (d, J = 8.3 Hz, 1H), 7.88
(d, J = 7.5 Hz, 1H), 7.64–7.52 (m, 4H), 7.49 (t, J = 7.8 Hz, 2H), 6.33
(dd, J = 6.1, 4.1 Hz, 1H), 3.50–3.41 (m, 2H), 3.39 (d, J = 4.8 Hz, 2H),
3.04 (dd, J = 13.8, 6.2 Hz, 1H), 2.96 (dd, J = 13.7, 4.0 Hz, 1H), 2.61
(s, 2H), 2.37–2.27 (m, 2H); 13C NMR (126 MHz, CDCl3) δ 199.0,
166.0, 134.9, 133.8, 133.4, 132.4, 130.2, 129.8, 129.4, 128.5,
128.3, 127.6, 126.8, 126.6, 125.9, 124.3, 76.6, 66.6, 58.8, 53.8.
HRMS (ESI): Calcd. for C24H24NO4 (M+H)+ 390.1700, found
390.1707.
61.9, 53.9, 38.4, 16.5.
4-Morpholino-2-oxoheptan-3-yl benzoate (3ra) was obtained
in 55% isolated yield, 3:1 dr (17.6 mg) as colorless oil. 1H NMR
(500 MHz, CDCl3) δ 8.09–8.03 (m, 2H), 7.65–7.58 (m, 1H),
7.54–7.45 (m, 2H), 5.45 (m, 4.1 Hz, 1H), 3.74–3.54 (m, 4H), 3.20
(m, 4.5 Hz, 1H), 2.99–2.69 (m, 2H), 2.65–2.49 (m, 2H), 2.23 (d, J =
4.7 Hz, 3H), 1.97–1.79 (m, 1H), 1.74–1.61 (m, 1H), 1.59–1.48 (m,
1H), 1.48–1.34 (m, 2H), 0.94 (dt, J = 10.4, 7.3 Hz, 3H); 13C NMR
(126 MHz, CDCl3) δ 205.7, 165.9, 133.6, 129.8, 129.4, 128.6, 81.3,
67.4, 64.7, 49.6, 28.9, 27.2, 20.2, 14.0. HRMS (ESI): Calcd. for
C18H26NO4 (M+H)+ 320.1856, found 320.1849.
4-Morpholino-2-oxooctan-3-yl benzoate (3sa) was obtained in
50% isolated yield, 4:1 dr (16.7 mg) as colorless oil. H NMR (500
1
Morpholino-3-oxobutan-2-yl benzoate (3ma) was obtained in
1
50% isolated yield (13.8 mg) as colorless oil. H NMR (500 MHz,
MHz, CDCl3) δ 8.05 (m, 1.2 Hz, 2H), 7.61 (m, 1.3 Hz, 1H), 7.48 (m,
3.0 Hz, 2H), 5.44 (dd, J = 13.1, 4.2 Hz, 1H), 3.72–3.56 (m, 4H), 3.18
(m, 4.4 Hz, 1H), 2.97–2.71 (m, 2H), 2.60–2.51 (m, 2H), 2.23 (d, J =
6.7 Hz, 3H), 1.93–1.82 (m, 1H), 1.71–1.60 (m, 1H), 1.53–1.39 (m,
2H), 1.39–1.24 (m, 4H), 0.96–0.83 (m, 3H); 13C NMR (126 MHz,
CDCl3) δ 205.7, 165.7, 133.6, 129.8, 129.4, 128.6, 78.1, 67.4, 65.0,
49.6, 29.3, 27.3, 26.7, 22.7, 13.9. HRMS (ESI): Calcd. for C19H28NO4
(M+H)+ 334.2013, found 334.2021.
4-Morpholino-2-oxononan-3-yl benzoate (3ta) was obtained in
60% isolated yield, 2.5:1 dr. (20.7 mg) as colorless oil. 1H NMR
(500 MHz, CDCl3) δ 8.10–8.01 (m, 2H), 7.64–7.57 (m, 1H),
7.53–7.45 (m, 2H), 5.44 (dd, J = 12.4, 4.2 Hz, 1H), 3.70–3.56 (m,
4H), 3.18 (m, 4.5 Hz, 1H), 2.98–2.70 (m, 2H), 2.61–2.50 (m, 2H),
2.23 (d, J = 6.1 Hz, 3H), 1.93–1.81 (m, 1H), 1.64 (m, 6.2 Hz, 1H),
1.58–1.48 (m, 1H), 1.48–1.35 (m, 2H), 1.35–1.24 (m, 5H), 0.87 (dt,
J = 12.0, 6.7 Hz, 3H); 13C NMR (126 MHz, CDCl3) δ 205.7, 165.7,
133.5, 129.7, 129.4, 128.6, 78.2, 67.4, 65.0, 49.6, 31.8, 27.3, 26.8,
23.5, 22.6, 14.0. HRMS (ESI): Calcd. for C20H30NO4 (M+H)+
348.2169, found 348.2178.
CDCl3) δ 8.14–7.99 (m, 2H), 7.68–7.55 (m, 1H), 7.53–7.40 (m, 2H),
5.43 (dd, J = 6.5, 3.8 Hz, 1H), 3.77–3.52 (m, 4H), 2.99 (dd, J = 13.9,
6.5 Hz, 1H), 2.88 (dd, J = 13.9, 3.8 Hz, 1H), 2.66 (dt, J = 9.4, 4.5 Hz,
2H), 2.57–2.49 (m, 2H), 2.28 (s, 3H); 13C NMR (126 MHz, CDCl3) δ
204.2, 165.8, 133.5, 129.8, 129.3, 128.6, 77.7, 66.9, 58.6, 54.0,
27.1. HRMS (ESI): Calcd. for C15H20NO4 (M+H)+ 278.1387, found
278.1392.
Morpholino-3-oxopentan-2-yl benzoate (3na) was obtained in
1
72% isolated yield (22.4 mg) as colorless oil. H NMR (500 MHz,
CDCl3) δ 8.11–8.00 (m, 2H), 7.68–7.55 (m, 1H), 7.52–7.39 (m, 2H),
5.45 (dd, J = 6.6, 3.9 Hz, 1H), 3.74–3.56 (m, 4H), 2.97 (dd, J = 13.8,
6.7 Hz, 1H), 2.86 (dd, J = 13.8, 3.9 Hz, 1H), 2.69–2.53 (m, 4H),
2.53–2.47 (m, 2H), 1.09 (t, J = 7.2 Hz, 3H); 13C NMR (126 MHz,
CDCl3) δ 207.0, 165.8, 133.4, 129.7, 129.4, 128.5, 67.0, 58.8, 54.0,
32.9, 7.2. HRMS (ESI): Calcd. for C16H22NO4 (M+H)+ 292.1543,
found 292.1552.
Morpholino-3-oxooctan-2-yl benzoate (3oa) was obtained in
1
63% isolated yield (20.9 mg) as colorless oil. H NMR (500 MHz,
CDCl3) δ 8.18–7.98 (m, 2H), 7.65–7.55 (m, 1H), 7.52–7.39 (m, 2H),
5.44 (dd, J = 6.6, 3.8 Hz, 1H), 3.74–3.55 (m, 4H), 2.98 (dd, J = 13.8,
6.6 Hz, 1H), 2.86 (dd, J = 13.8, 3.8 Hz, 1H), 2.69–2.62 (m, 2H),
2.61–2.48 (m, 4H), 1.68–1.59 (m, 2H), 1.35–1.27 (m, 4H)
0.98–0.82 (m, 3H); 13C NMR (126 MHz, CDCl3) δ 206.3, 165.78,
133.4, 129.7, 129.4, 128.5, 77.3, 66.9, 58.7, 54.0, 39.5, 31.3, 22.7,
22.4, 13. 9. HRMS (ESI): Calcd. for C19H28NO4 (M+H)+ 334.2013,
found 334.2019.
4-Morpholino-2-oxodecan-3-yl benzoate (3ua) was obtained
in 52% isolated yield, 2.5:1 dr (18.9 mg) as colorless oil. H NMR
1
(500 MHz, CDCl3) δ 8.05 (m, 2H), 7.61 (m, 1H), 7.49 (m, 2H), 5.44
(dd, J = 11.5, 4.2 Hz, 1H), 3.69–3.56 (m, 4H), 3.29–3.07 (m, 1H),
2.97–2.70 (m, 2H), 2.62–2.51 (m, 2H), 2.23 (d, J = 6.5 Hz, 3H), 1.88
(m, 1H), 1.73–1.60 (m, 1H), 1.46 (m, 1H), 1.39–1.22 (m, 6H),
0.95–0.79 (m, 3H); 13C NMR (126 MHz, CDCl3) δ 205.7, 165.7,
133.5, 129.8, 129.4, 128.6, 78.1, 67.4, 65.0, 49.6, 31.7, 29.7, 27.3,
26.8, 23.5, 22.6, 14.0. HRMS (ESI): Calcd. for C21H32NO4 (M+H)+
362.2326, found 362.2333.
3-Morpholino-1-oxo-1,2-diphenylpropan-2-yl benzoate (3pa)
1
was obtained in 54% isolated yield (22.3 mg) as colorless solid. H
NMR (500 MHz, CDCl3) δ 8.08 (dd, J = 8.2, 1.2 Hz, 2H), 7.79 (dd, J =
8.4, 1.1 Hz, 2H), 7.73 (d, J = 7.4 Hz, 2H), 7.63–7.57 (m, 1H), 7.46
(dt, J = 17.1, 8.0 Hz, 4H), 7.38–7.33 (m, 1H), 7.32–7.27 (m, 1H),
7.18 (dd, J = 10.8, 4.8 Hz, 2H), 3.83 (d, J = 14.5 Hz, 1H), 3.34 (dd, J
= 9.3, 4.6 Hz, 4H), 2.32–2.24 (m, 2H), 2.21–2.14 (m, 2H); 13C NMR
1-Oxo-1-phenyl-3-(piperidin-1-yl)propan-2-yl benzoate (3ab)
was obtained in 82% isolated yield (27.8 mg) as colorless solid. H
1
NMR (400 MHz, CDCl3) δ 8.10 (d, J = 8.0 Hz, 2H), 8.04 (d, J = 7.9 Hz,
2H), 7.58 (td, J = 7.1, 0.9 Hz, 2H), 7.53–7.43 (m, 4H), 6.33–6.26 (m,
1H), 3.09–2.93 (m, 2H), 2.62–2.44 (m, 4H), 1.54–1.43 (m, 4H),
(126 MHz, CDCl3) δ 196.8, 165.0, 138.2, 135.1, 133.4, 132.2, 130.1, 1.41–1.33 (m, 2H); 13C NMR (101 MHz, CDCl3) δ 196.0, 166.0,
129.6, 129.0, 128.7, 128.6, 128.1, 128.0, 125.1, 88.1, 67.1, 63.5,
54.5. HRMS (ESI): Calcd. for C26H26NO4 (M+H)+ 416.1856, found
416.1869.
135.3, 133.3, 133.2, 129.8, 129.5, 128.6, 128.4, 128.4, 74.4, 59.3,
54.7, 25.9, 23.9. HRMS (ESI): Calcd. for C21H23NNaO3 (M+Na)+
360.1570, found 360.1572.
2-methyl-3-morpholino-1-phenylpropan-1-one (4qa) was
3-(4-Methylpiperidin-1-yl)-1-oxo-1-phenylpropan-2-yl
1
obtained in 52% isolated yield (12.2 mg) as colorless oli. H NMR
benzoate (3ac) was obtained in 74% isolated yield (26.0 mg) as
colorless solid. 1H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 7.6 Hz, 2H),
8.03 (d, J = 7.7 Hz, 2H), 7.59 (dd, J = 7.8, 5.8 Hz, 2H), 7.47 (dt, J =
15.2, 7.7 Hz, 4H), 6.29 (dd, J = 6.2, 4.7 Hz, 1H), 3.07–3.00 (m, 2H),
2.96 (d, J = 12.2 Hz, 1H), 2.89 (d, J = 11.0 Hz, 1H), 2.19 (td, J = 11.3,
(400 MHz, CDCl3) δ 7.95 (dd, J = 5.2, 3.4 Hz, 1H), 7.63 – 7.36 (m,
3H), 3.84 – 3.67 (m, 2H), 3.61 (dd, J = 6.6, 2.6 Hz, 4H), 2.86 (dd, J =
12.5, 7.8 Hz, 1H), 2.51 – 2.40 (m, 4H), 1.20 (d, J = 7.0 Hz, 2H). 13C
NMR (101 MHz, CDCl3) δ 203.7, 132.9, 128.6, 128.2, 127.1, 66.9,
Chin. J. Chem. 2019, 37, XXX-XXX
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