双齿含氧配体修饰Co2(CO)8催化环氧丙 (乙) 烷羰化酰胺化反应制备β-羟基酰胺

doi:10.3969/j.issn.1000-5641.2023.01.002

摘要/Abstract

摘要：

首次报道了以芳香胺为氨源, 通过双齿含氧配体L2修饰Co₂(CO)₈催化环氧化合物的羰化酰胺化反应, 一步合成β-羟基酰胺化合物的方法. 在温和的条件下 (60℃、CO 3.0 MPa、6 h), 以L2修饰的Co₂(CO)₈作为催化剂, 能够实现环氧丙烷和苯胺的羰化酰胺化反应, 得到收率为64%的3-羟基-N-苯基丁酰胺目标产物; 该催化剂体系具有较好的稳定性和一定的底物普适性. 其中, 双齿含氧配体L2通过双氧水氧化双齿膦配体Xantphos (9,9-二甲基-4,5-双二苯基膦-氧杂蒽) 制得.

关键词: 环氧丙烷, 环氧乙烷, 羰化酰胺化反应, Co₂(CO)₈, β-羟基酰胺

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

中图分类号:

O643

郭琳, 时广辉, 陈晓超, 刘晔. 双齿含氧配体修饰Co₂(CO)₈催化环氧丙 (乙) 烷羰化酰胺化反应制备β-羟基酰胺[J]. 华东师范大学学报（自然科学版）, 2023, 2023(1): 12-20.

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.

图/表 6

图1

表1

反应产物3a—3i的 1H NMR和 13C NMR光谱表征数据"

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

表1

表2

表3

图2

图3

参考文献 27

1	VAN LEEUWEN P W N M, CHADWICK J C. Homogeneous Catalysts: Activity-Stability-Deactivation [M]. Weinheim, Germany: Wiley-VCH, 2011: 244-277.
2	KOLLÁR L. Modern Carbonylation Methods [M]. Weinheim, Germany: Wiley-VCH, 2008.
3	樊启佳, 刘建华, 陈静, 等. 环氧化合物羰基化反应研究新进展. 催化学报, 2012, 33, 1435- 1447.
4	TSUJI Y, KOBAYASHI M, OKUDA F, et al. Cobalt catalyzed ring-opening carbonylation of cyclic ethers using N-(trimethylsilyl)amines[J]. Chemical Communications, 1989, 17: 1253-1254.
5	WATANABE Y, NISHIYAMA K, ZHANG K, et al. Co₂(CO)₈-catalyzed ring-opening carbonylation of cyclic ethers using N-silylamines[J]. Bulletin of the Chemical Society of Japan, 1994, 67: 879-882.
6	MURAI T, YASUI E, KATO S, et al. Cobalt carbonyl-catalyzed reactions of cyclic ethers with a hydrosilane and carbon monoxide. A new synthetic reaction equivalent to nucleophilic oxymethylation. Journal of the American Chemical Society, 1989, 111 (20): 7938- 7946.
7	MURAI T, KATO S, MURAI S, et al. Oxymethylative opening of oxiranes leading to 1,3-diol derivatives by cobalt carbonyl catalyzed reaction with a hydrosilane and carbon monoxide. Journal of the American Chemical Society, 1984, 106, 6093- 6095.
8	GOODMAN S N, JACOBSEN E N. Enantiopure beta-hydroxy morpholine amides from terminal epoxides by carbonylation at 1 atm. Angewandte Chemie-International Edition, 2002, 41, 4703- 4705.
9	HINTERDING K, JACOBSEN E N. Regioselective carbomethoxylation of chiral epoxides: A new route to enantiomerically pure β-hydroxy esters. Journal of Organic Chemistry, 1999, 64, 2164- 2165.
10	BALÁZS A, BENEDEK C, SZALONTAI G, et al. Selective ring-opening carbonylation of epoxy-steroids. Steroids, 2004, 69, 271- 277.
11	TUBA R, MIKA L T, BODOR A, et al. Mechanism of the pyridine-modified cobalt-catalyzed hydromethoxycarbonylation of 1,3-butadiene. Organometallics, 2003, 22, 1582- 1584.
12	ALLMENDINGER M, EBERHARDT R, LUINSTRA G, et al. The cobalt-catalyzed alternating copolymerization of epoxides and carbon monoxide: A novel approach to polyesters. Journal of the American Chemical Society, 2002, 124, 5646- 5647.
13	刘建华, 陈静, 孙伟, 等. 若干羰基化反应研究新进展. 催化学报, 2010, 31, 1- 11.
14	LIU J H, WU H, XU L W, et al. A novel and highly effective catalytic system for alkoxycarbonylation of (S)-propylene oxide . Journal of Molecular Catalysis A: Chemical, 2007, 269, 97- 103.
15	HAMASAKI A, MUTO A, HARAGUCHI S, et al. Cobalt oxide supported gold nanoparticles as a stable and readily-prepared precursor for the in situ generation of cobalt carbonyl like species. Tetrahedron Letters, 2011, 52, 6869- 6872.
16	DENG F G, HU B, SUN W, et al. Novel pyridinium based cobalt carbonyl ionic liquids: Synthesis, full characterization, crystal structure and application in catalysis. Dalton Transaction, 2007, 38, 4262- 4267.
17	LYU Z G, WANG H S, LI J, et al. Hydroesterification of ethylene oxide catalyzed by 1-butyl-3-methylimidazolium cobalt tetracarbonyl ionic liquid. Research on Chemical Intermediates, 2010, 36, 1027- 1035.
18	GUO Z M, WANG H S, LUY Z G, et al. Catalytic performance of [Bmim][Co(CO)₄] functional ionic liquids for preparation of 1,3-propanediol by coupling of hydroesterification-hydrogenation from ethylene oxide . Journal of Organometallic Chemistry, 2011, 696, 3668- 3672.
19	ZHANG W, HAN F, TONG J, et al. Cobalt carbonyl ionic liquids based on the 1,1,3,3-tetra-alkylguanidine cation: Novel, highly efficient, and reusable catalysts for the carbonylation of epoxides. Chinese Journal of Catalysis, 2017, 38, 805- 812.
20	MCCLURE J D, FISHER R F. Hydracrylic acid esters: US 3260738 [P]. 1966-07-12.
21	FAWCETT J, PLATT A W G, VICKERS S, et al. Lanthanide halide and nitrate complexes with potentially tridentate bisphosphine dioxide-ether donors. Polyhedron, 2004, 23 (16): 2561- 2567.
22	HORIBE T, SAKAKIBARA M, HIRAMATSU R, et al. One-pot tandem michael addition/enantioselective conia-ene cyclization mediated by chiral iron(Ⅲ)/silver( Ⅰ ) cooperative catalysis. Angewandte Chemie-International Edition, 2020, 59, 16470- 16474.
23	XU J X, WU X F. Cobalt-catalyzed alkoxycarbonylation of epoxides to β-hydroxyesters. Journal of Organic Chemistry, 2019, 84, 9907- 9912.
24	ZENG B, LIU M L, HE J H, et al. On the origin of nitrogen-containing promoters in the cobalt-catalyzed methoxycarbonylation of epoxides [J]. Applied Catalysis A: General, 2021, 623: 118291.
25	ALLMENDINGER M, ZINTL M, EBERHARDT R, et al. Online ATR-IR investigations and mechanistic understanding of the carbonylation of epoxides-the selective synthesis of lactones or polyesters from epoxides and CO. Journal of Organometallic Chemistry, 2004, 689, 971- 979.
26	LIU J H, CHEN J, XIA C G. Methoxycarbonylation of propylene oxide: A new way to β-hydroxybutyrate. Journal of Molecular Catalysis A: Chemical, 2006, 250, 232- 236.
27	WEBER R, ENGLERT U, GANTER B, et al. Hydroformylation of epoxides catalyzed by cobalt and hemilabile P-O ligands. Chemical Communications, 2000, 1419- 1420.


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

[1]	王浩, 赵国锋, 路勇. 乙醇酸甲酯选择性氧化制备乙醛酸甲酯研究进展[J]. 华东师范大学学报（自然科学版）, 2023, 2023(1): 104-113.
[2]	李梦楠, 信惠跃, 吴鹏, 李晓红. 负载型铂基催化剂在肉桂醛选择加氢中的研究进展[J]. 华东师范大学学报（自然科学版）, 2023, 2023(1): 114-128.
[3]	汤静, 张子宁, 郑翔. 铜基催化剂在电还原二氧化碳领域的应用研究[J]. 华东师范大学学报（自然科学版）, 2023, 2023(1): 149-159.
[4]	赵磊, 李泽霖, 李愽龙, 边树昌, 王建华, 张海兰, 赵晨. 生物基2,5-呋喃二甲酸的绿色合成技术综述[J]. 华东师范大学学报（自然科学版）, 2023, 2023(1): 160-169.
[5]	马跃, 徐浩, 刘月明, 张坤, 吴鹏, 何鸣元. 沸石孔道限域亚纳米金属团簇催化剂研究进展[J]. 华东师范大学学报（自然科学版）, 2023, 2023(1): 82-94.
[6]	高雅, 孙伟东, 赵国锋, 刘晔, 路勇. 化学链甲烷氧化偶联载氧体催化剂Na₂WO₄/Mn₇SiO₁₂-SiO₂的研究[J]. 华东师范大学学报（自然科学版）, 2023, 2023(1): 95-103.
[7]	陈加祥, 张哲娟, 聂耳, 宋也男, 朴贤卿, 孙卓. I-TiO₂/Sr₂MgSi₂O₇:Eu,Dy复合光催化剂的制备及性能研究[J]. 华东师范大学学报（自然科学版）, 2022, 2022(6): 157-168.
[8]	吴玮;郁可;朱自强. 基于聚苯乙烯模板的二维光子晶体的制备[J]. 华东师范大学学报(自然科学版), 2010, 2010(5): 103-109.
[9]	董鹏飞;韩婧;邵启伟;成荣明. ZnO纳米棒/PVC复合材料的光催化性能研究[J]. 华东师范大学学报(自然科学版), 2009, 2009(5): 29-39,8.

双齿含氧配体修饰Co₂(CO)₈催化环氧丙 (乙) 烷羰化酰胺化反应制备β-羟基酰胺

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

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 27

相关文章 9

编辑推荐

Metrics

本文评价


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