过氧化氢原位生成驱动过氧合酶催化反应研究进展

doi:10.6023/cjoc202108052

摘要/Abstract

C—H键的选择性催化氧官能团化反应是有机化学中非常具有挑战的一类反应. 与贵金属络合物催化剂相比, 生物酶在选择性和活性等方面表现出一定优势. 其中, 过氧合酶(peroxygenase)作为近年来研究热点, 能够直接利用过氧化氢(H₂O₂)作为共底物催化C—H键的氧官能团化反应. 过氧合酶结合了P450单加氧酶的催化多功能性且无须依赖辅酶及其再生体系, 因此在有机合成中引起越来越多的重视. 但是, 过氧合酶在实际应用中存在一个瓶颈: 即过氧合酶对其催化所必须的H₂O₂浓度敏感, 当反应体系中H₂O₂浓度过高时, 会引起过氧合酶中的亚铁血红素氧化分解, 从而导致酶失活. 为突破该瓶颈, 调控反应体系中H₂O₂的浓度对于高效应用过氧合酶来说格外重要. 概括了近年来多种原位生成H₂O₂驱动过氧合酶催化的方法. 从酶催化、光催化、电催化原位生成H₂O₂角度出发, 全面分析了近年来开发的高原子经济性H₂O₂原位生成技术驱动过氧合酶催化体系的优缺点, 为促进该酶在有机合成中的应用提供参考.

关键词: 过氧合酶, H₂O₂原位生成, 碳氢键氧官能团化, 生物催化, 有机合成

Selective catalytic oxygen functionalization reactions of C—H bonds are a very challenging class of reactions in organic chemistry. Compared with tranditional metal complex catalysts, enzymes exhibit certain advantages in terms of selectivity and activity. Amongest them, peroxygenases are able to catalyze the oxidative functionalization of C—H bonds by direct use of H₂O₂ as a co-substrate. Peroxygenases combine the catalytic versatility of P450 monooxygenases without relying on coenzymes and their regenerative systems for cofactors. Therefore, peroxygenases have attracted considerable attention in organic synthesis. However, a bottleneck in the practical application of peroxygenase is that, like all heme-dependent enzymes, peroxygenase is sensitive to H₂O₂, and higher concentration of H₂O₂ in the reaction system will cause oxidative decomposition of ferrous heme, resulting in the enzyme inactivation. To overcome this, regulating the concentration of H₂O₂ in the reaction is particularly important for the efficient use of peroxygenase. This paper outlines a variety of methods used for in situ generation of H₂O₂ to drive peroxygenases reported in recent years. The pros and cons of biocatalysis, photocatalysis and electrocatalysis used for high atom-efficient H₂O₂ generation are comprehensively analyzed. This review paper is expected to provide a reference for promoting the application of peroxygenases in organic synthesis.

Key words: peroxygenase, H₂O₂ in situ generation, C—H bond oxyfunctionalization, biocatalysis, organic synthesis

引用此文

李可欣, 杨庆远, 张鹏鹏, 张武元. 过氧化氢原位生成驱动过氧合酶催化反应研究进展[J]. 有机化学, 2022, 42(3): 732-741.

Kexin Li, Qingyuan Yang, Pengpeng Zhang, Wuyuan Zhang. Research Progress of Peroxygenase-Catalyzed Reactions Driven by in-situ Generation of H₂O₂[J]. Chinese Journal of Organic Chemistry, 2022, 42(3): 732-741.

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图/表 14

图1. P450单加氧酶(a)和过氧合酶(b)催化的C—H键氧官能团化反应

Figure 1. P450 monooxygenase (a) and peroxygenase (b) catalyzed C—H bond oxyfunctionalization reactions

图2. 过氧合酶催化C―H键的选择性活化及转化

Figure 2. Selective activation and transformation of C―H bonds catalyzed by peroxygenases

年份	原位生成H₂O₂方式	催化剂/电极	酶	底物	产物	ee^a/%	TON/TTN^b	Ref.
2000		葡萄糖氧化酶	CPO (氯过氧化物 Chloroperoxidase)	硫代苯甲醚	(R)-苯甲基亚砜	99	250000	[14]
2002		D-氨基酸	CiP (来自灰盖鬼伞菌的过氧合酶, peroxidase from Coprinus cinereus)	(三种)芳香甲基硫化物	(三种)芳甲基亚砜	97	>500	[18]
2007		甲醇氧化酶	CiP	硫代苯甲醚	(R)-苯甲基亚砜	75左右	>700	[20]
2014		甲酸脱氢酶、 NADH氧化酶	HRP (辣根过氧合酶, peroxidase from horseradish)	乙苯	(R)-1-苯乙醇	—	6785	[21]
2015	酶催化	甲醇氧化酶、甲醛歧化酶、 NADH氧化酶、甲酸脱氢酶、 3-羟基苯甲酸- 6-羟化酶	AaeUPO (真菌过加氧酶, The unspecific peroxygenase from Agrocybe aegerita)	乙苯	(R)-1-苯乙醇	>99	294700	[23]
2018		NADH氧化酶、 YqjM	rAaeUPO (重组真菌过加氧酶, recombinant peroxygenase from Agrocybe aegerita)	乙苯	(R)-1-苯乙醇	>96	390000	[25]
2020		甲酸氧化酶	rAaeUPO	乙苯环己烷顺式β-甲基苯乙烯	(R)-1-苯乙醇环己醇 (1R,2S)-顺-β- 甲基苯乙烯	97.5	49000	[27]
2009		黄素单核苷酸	CPO	硫代苯甲醚	(R)-苯甲基亚砜	<99	22000	[29]
2013		黄素单核苷酸	CPO	硫代苯甲醚	(R)-苯甲基亚砜	>96	12600	[31]
2017		Au-TiO₂	rAaeUPO	乙苯	(R)-1-苯乙醇	>98	>71000	[32]
2019	光催化	石墨相氮化碳g-C₃N₄	rAaeUPO	乙苯	(R)-1-苯乙醇	>97.8	60000	[35]
2019		酚藏红花、亚甲基蓝、黄素单核苷酸	rAaeUPO	乙苯	(R)-1-苯乙醇	>95	100000	[36]
2020		水溶性蒽醌磺酸钠	CiVCPO; rAaeUPO	百里香酚乙苯环己烷苯乙烯 4-戊烯酸	卤化百里香酚 (R)-1-苯乙醇环己醇, 环己酮 1-苯基-2-溴乙醇氧化苯乙烯 4-溴甲基环戊内酯	34	318000; 177000	[37]
2004		碳基电极	CPO	硫代苯甲醚	(R)-苯甲基亚砜	>98.5	95000	[39]
2006		碳基电极	CPO	三种底物	三种产物	93、99	58900 64400 7000	[40]
2007		碳基电极	CPO	硫代苯甲醚	(R)-苯甲基亚砜	98.5	145000	[41]
2011	电催化	GDE电极	CPO	单氯二甲醚硫代苯甲醚吲哚	二氯二甲醚 (R)-苯甲基亚砜羟吲哚	—	203100 83600 39000	[43]
2014		GDE电极	CPO	一氯二甲酮	二氯二甲酮	—	1150000	[44]
2017		黄素-SWNT 电极	AaeUPO	乙苯 2-苯氧基丙酸吲哚	(R)-1-苯乙醇	95%	123900±7290 5900±210 4900±340	[46]
2019		氧化碳纳米管	CiVCPO	4-戊烯酸	溴内酯	—	—	[48]

年份	原位生成H₂O₂方式	催化剂/电极	酶	底物	产物	ee^a/%	TON/TTN^b	Ref.
2000		葡萄糖氧化酶	CPO (氯过氧化物 Chloroperoxidase)	硫代苯甲醚	(R)-苯甲基亚砜	99	250000	[14]
2002		D-氨基酸	CiP (来自灰盖鬼伞菌的过氧合酶, peroxidase from Coprinus cinereus)	(三种)芳香甲基硫化物	(三种)芳甲基亚砜	97	>500	[18]
2007		甲醇氧化酶	CiP	硫代苯甲醚	(R)-苯甲基亚砜	75左右	>700	[20]
2014		甲酸脱氢酶、 NADH氧化酶	HRP (辣根过氧合酶, peroxidase from horseradish)	乙苯	(R)-1-苯乙醇	—	6785	[21]
2015	酶催化	甲醇氧化酶、甲醛歧化酶、 NADH氧化酶、甲酸脱氢酶、 3-羟基苯甲酸- 6-羟化酶	AaeUPO (真菌过加氧酶, The unspecific peroxygenase from Agrocybe aegerita)	乙苯	(R)-1-苯乙醇	>99	294700	[23]
2018		NADH氧化酶、 YqjM	rAaeUPO (重组真菌过加氧酶, recombinant peroxygenase from Agrocybe aegerita)	乙苯	(R)-1-苯乙醇	>96	390000	[25]
2020		甲酸氧化酶	rAaeUPO	乙苯环己烷顺式β-甲基苯乙烯	(R)-1-苯乙醇环己醇 (1R,2S)-顺-β- 甲基苯乙烯	97.5	49000	[27]
2009		黄素单核苷酸	CPO	硫代苯甲醚	(R)-苯甲基亚砜	<99	22000	[29]
2013		黄素单核苷酸	CPO	硫代苯甲醚	(R)-苯甲基亚砜	>96	12600	[31]
2017		Au-TiO₂	rAaeUPO	乙苯	(R)-1-苯乙醇	>98	>71000	[32]
2019	光催化	石墨相氮化碳g-C₃N₄	rAaeUPO	乙苯	(R)-1-苯乙醇	>97.8	60000	[35]
2019		酚藏红花、亚甲基蓝、黄素单核苷酸	rAaeUPO	乙苯	(R)-1-苯乙醇	>95	100000	[36]
2020		水溶性蒽醌磺酸钠	CiVCPO; rAaeUPO	百里香酚乙苯环己烷苯乙烯 4-戊烯酸	卤化百里香酚 (R)-1-苯乙醇环己醇, 环己酮 1-苯基-2-溴乙醇氧化苯乙烯 4-溴甲基环戊内酯	34	318000; 177000	[37]
2004		碳基电极	CPO	硫代苯甲醚	(R)-苯甲基亚砜	>98.5	95000	[39]
2006		碳基电极	CPO	三种底物	三种产物	93、99	58900 64400 7000	[40]
2007		碳基电极	CPO	硫代苯甲醚	(R)-苯甲基亚砜	98.5	145000	[41]
2011	电催化	GDE电极	CPO	单氯二甲醚硫代苯甲醚吲哚	二氯二甲醚 (R)-苯甲基亚砜羟吲哚	—	203100 83600 39000	[43]
2014		GDE电极	CPO	一氯二甲酮	二氯二甲酮	—	1150000	[44]
2017		黄素-SWNT 电极	AaeUPO	乙苯 2-苯氧基丙酸吲哚	(R)-1-苯乙醇	95%	123900±7290 5900±210 4900±340	[46]
2019		氧化碳纳米管	CiVCPO	4-戊烯酸	溴内酯	—	—	[48]

表1. 原位生成H2O2驱动过氧合酶催化反应对比表

Table 1. Comparison of in situ H2O2 generation used for driving peroxygenase

表1. 原位生成H2O2驱动过氧合酶催化反应对比表

Table 1. Comparison of in situ H2O2 generation used for driving peroxygenase

图3. 酶催化原位生成H2O2驱动过氧合酶催化选择性氧官能团化反应

Figure 3. Peroxygenase-catalyzed selective oxyfunctionalization reactions driven by enzymatic in situ H2O2 generation

图4. 多酶偶联催化甲醇的彻底氧化并释放3 equiv.的H2O2

Figure 4. Multi-enzyme cascade used for complete methanol oxidation to CO2 in releasing 3 equiv. of H2O2

图5. FDH、YqjM和NADH三者结合原位生成H2O2驱动rAaeUPO对乙苯进行羟基化反应

Figure 5. rAaeUPO-catalyzed hydroxylation of ethylbenzene driven by H2O2 in situ generated via the combination of FDH, YqjM and NADH

图6. 新型甲酸氧化酶AoFOx原位生成H2O2驱动不同的生物酶催化多类型反应

Figure 6. Novel formic acid oxidase AoFOx used for in situ H2O2 generation and its combination with various enzymes

图7. 光催化原位生成H2O2驱动过氧合酶反应过程(在光照激发下光催化剂被活化, 氧化底物1(即电子牺牲剂), 从而将O2还原为H2O2驱动过氧合酶)

Figure 7. Photocatalytic in situ generation of H2O2 used for driving peroxygenase-catalyzed reactions (photocatalyst is activated under light excitation to oxidize substrate 1 (namely electron sacrificial agent), thereby reducing O2 to H2O2 to drive peroxygenase-catalyzed reactions)

图8. 2LPS反应体系原位生成H2O2驱动CPO催化亚砜化反应

Figure 8. 2LPS reaction system used for in situ generation of H2O2 and promoting CPO-catalyzed sulfoxidation reaction

图9. Au-TiO2作光催化剂原位生成H2O2驱动rAaeUPO进行羟基化反应

Figure 9. rAaeUPO-catalyzed hydroxylation reactions driving by Au-TiO2 as photocatalyst for in situ H2O2 generation

图10. 电催化原位生成H2O2驱动过氧合酶反应过程

Figure 10. Peroxygenase-catalyzed reaction process driven by electrocatalytic in situ H2O2 generation

图11. 使用GDE电极电催化原位生成H2O2驱动CPO催化反应

Figure 11. CPO-catalyzed reactions driven by electrocatalysis using GDE electrode

图12. LC-SWNT电极原位生成H2O2驱动CiVCPO选择性催化氧化反应过程

Figure 12. CiVCPO-catalyzed selective oxidation reactions driven by H2O2 in situ generated on LC-SWNT electrode

图13. scCO2/H2O双相介质中原位生成H2O2驱动CPO催化选择性氧化反应

Figure 13. CPO-catalyzed selective oxidation reactions driven by H2O2 in situ generated in scCO2/H2O biphasic medium

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