Aminocarbonylation of propylene (ethylene) epoxide over Co2(CO)8 catalyst modified by bidental O-containing ligand for synthesis of β-hydroxy amides

doi:10.3969/j.issn.1000-5641.2023.01.002

Abstract

Abstract:

This work reports a one-step protocol for the synthesis of β-hydroxyamides via amino-carbonylation of epoxides using aromatic amines as the ammonia source instead of silylamine. The reaction was catalyzed by Co₂(CO)₈ modified with bidentate O-containing ligand L2, which was prepared by the oxidation of Xantphos [9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene] by H₂O₂ as a diphosphine-dioxide. Under mild conditions (60 °C, CO 3.0 MPa, 6 h), L2-modified Co₂(CO)₈ efficiently catalyzed the amino-carbonylation of propylene oxide with aniline to generate 3-hydroxy-N-phenylbutanamide with the yield of 64%. The developed catalytic system exhibited fair stability and general substrate scope.

Key words: propylene oxide, ethylene oxide, aminocarbonylation, Co₂(CO)₈, β-hydroxy amides

CLC Number:

O643

Lin GUO, Guanghui SHI, Xiaochao CHEN, Ye LIU. Aminocarbonylation of propylene (ethylene) epoxide over Co₂(CO)₈ catalyst modified by bidental O-containing ligand for synthesis of β-hydroxy amides[J]. Journal of East China Normal University(Natural Science), 2023, 2023(1): 12-20.

Figures/Tables 6

Fig.1

Table 1

1H NMR and 13C NMR results for products 3a—3i"

化合物	¹H NMR (500 MHz, CDCl₃), δ	¹³C NMR (126 MHz, CDCl₃), δ
3a	7.93 (s, 1H), 7.53 ~ 7.47 (m, 2H), 7.33 ~ 7.30 (m, 2H), 7.14 ~ 7.10 (m, 1H), 4.33 ~ 4.27 (m, 1H), 2.97 (s, 1H), 2.54 ~ 2.42 (m, 2H), 1.28 (d,J= 6.5 Hz, 3H)	137.53, 129.03, 124.51, 120.10, 120.07, 77.23, 64.99, 45.18, 23.05
3b	7.76 (s, 1H), 7.38 ~ 7.36 (m, 2H), 7.13 ~ 7.11 (m, 2H), 4.32 ~ 4.26 (m, 1H), 2.85 (s, 1H), 2.53 ~ 2.43 (m, 2H), 2.31 (s, 3H), 1.28 (d, J= 6.0 Hz, 3H)	170.38, 134.92, 134.20, 129.51, 120.19, 64.98, 45.04, 22.98, 20.88
3c	7.82 (d, J= 8.0, 2H), 7.24 ~ 7.15 (m, 2H), 7.07 (m, 1H), 4.32 ~ 4.29 (m, 1H), 2.74 (s, 1H), 2.59 ~ 2.48 (m, 2H), 2.25 (s, 3H), 1.31 (d, J= 6.0 Hz, 3H)	170.48, 135.53, 130.48, 129.01, 126.74, 125.22, 123.07, 65.07, 45.04, 23.19, 17.89
3d	7.74 (s, 1H), 7.39 (d, J= 8.5 Hz, 2H), 6.85 (d, J = 8.5 Hz, 2H), 4.30 ~ 4.28 (m, 1H), 3.78 (s, 3H), 2.74 (s, 1H), 2.52 ~ 2.41 (m, 2H), 1.28 (d, J= 6.5 Hz, 3H)	170.42, 156.58, 130.55, 122.04, 114.17, 64.99, 55.50, 44.90, 23.02
3e	8.30 (dd, J = 10.0, 6.0 Hz, 1H), 8.19 (s, 1H), 7.03 (m, 1H), 6.93 (m, 1H), 6.86 (m, 1H), 4.32 ~ 4.22 (m, 1H), 3.86 (d, 1H), 3.85 (s, 3H), 2.56 ~ 2.46 (m, 2H), 1.26 (d, J= 6.5 Hz, 3H)	170.54, 148.03, 127.27, 124.02, 121.01, 120.15, 110.07, 64.86, 55.72, 45.43, 22.82
3f	8.02 (s, 1H), 7.47 ~ 7.43 (m, 2H), 7.03 ~ 6.98 (m, 2H), 4.32 ~ 4.26 (m, 1H), 3.05 (s, 1H), 2.54 ~ 2.43 (m, 2H), 1.28 (d, J= 5.0 Hz, 3H)	170.43, 159.45 (d, J= 244.4 Hz, 1C), 133.55, 121.94 (d, J= 7.5 Hz, 1C), 115.65 (d, J = 22.5 Hz,1C), 64.99, 45.03, 23.10
3g	7.93 (s, 1H), 7.46 ~ 7.38 (m, 4H), 4.30 (m, 1H), 2.57 ~ 2.45 (m, 2H), 2.38 (s, 1H), 1.30 (d, J= 6.0 Hz, 3H)	170.26, 136.69, 131.98, 121.52, 116.98, 64.99, 45.30, 23.16
3h	7.43 (m, 2H), 7.39 ~ 7.32 (m, 1H), 7.21 ~ 7.13 (m, 2H), 4.15 ~ 4.07 (m, 1H), 3.26 (s, 3H), 2.22 ~ 2.06 (m, 2H), 1.06 (d, J = 6.0 Hz, 3H)	172.94, 143.39, 129.96, 128.13, 127.24, 64.55, 41.80, 37.09, 22.23
3i	7.87 (s, 1H), 7.52 ~ 7.49 (m, 2H), 7.33 ~ 7.30 (m, 2H), 7.13 ~ 7.01 (m, 1H), 3.98 (t, J= 5.4 Hz, 2H), 2.62 (t, J= 5.4 Hz, 2H), 2.53 (s, 1H)	170.69, 137.58, 129.03, 124.51, 120.07, 58.82, 39.16

Table 1

Table 2

Table 3

Fig.2

Fig.3

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序号	(n_L2/n_Co₂_(CO)₈)/(mol%)	溶剂(v/v)	温度/℃	CO压力/MPa	时间/h	苯胺转化率^a/%	3a收率^a,b/%
1	1 : 1	四氢呋喃	60	3	6	70	39
2	1 : 1	1,4-二氧六环	60	3	6	55	41
3	1 : 1	四氢呋喃/1,4-二氧六环 (1/1)	60	3	6	83	64
4	1 : 1	四氢呋喃/1,4-二氧六环 (1/1)	40	3	6	30	14
5	1 : 1	四氢呋喃/1,4-二氧六环 (1/1)	80	3	6	84	57
6	1 : 1	四氢呋喃/1,4-二氧六环 (1/1)	60	4	6	58	37
7	1 : 1	四氢呋喃/1,4-二氧六环 (1/1)	60	3	4	37	25
8	1 : 1	四氢呋喃/1,4-二氧六环 (1/1)	60	3	8	84	65
9	1 : 2	四氢呋喃/1,4-二氧六环 (1/1)	60	3	6	53	24
10	2 : 1	四氢呋喃/1,4-二氧六环 (1/1)	60	3	6	65	40
11^c		四氢呋喃/1,4-二氧六环 (1/1)	80	3	6	60

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Aminocarbonylation of propylene (ethylene) epoxide over Co₂(CO)₈ catalyst modified by bidental O-containing ligand for synthesis of β-hydroxy amides

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序号	配体	苯胺转化率^a/%	3a收率^a/%
1		82	41
2	L1	90	42
3^b	L2	83	64
4	L3	32	6
5	L4	67	31
6	L5	88	52
7	L6	95	49