非血红素三价铁-单酰胺配合物催化简单烷烃亚甲基选择氧化

doi:10.6023/cjoc202504021

摘要/Abstract

报道了一种利用非血红素三价铁-单酰胺配合物催化以双氧水(H₂O₂)为氧化剂的简单烷烃亚甲基选择氧化反应.反应机理研究表明, 五价铁-氧物种作为活性中间体, 通过氢原子攫取(HAA)这一决速步骤实现C—H键活化.

The methylene-selective oxidation of simple alkanes catalyzed by a nonheme iron(III)-monoamidate complex using H₂O₂ as the terminal oxidant is reported. Mechanistic studies suggest that iron(V)-oxo species is the active intermediate, undergoing hydrogen atom abstraction (HAA) as the rate-determining step to initiate C—H bond activation.

Key words: biomimetic catalysis, nonheme iron complex, C—H oxidation

引用此文

陈亚诞, 黄嵩港, 陈洁, 王斌. 非血红素三价铁-单酰胺配合物催化简单烷烃亚甲基选择氧化[J]. 有机化学, 2025, 45(12): 4453-4462.

Yadan Chen, Songgang Huang, Jie Chen, Bin Wang. Nonheme Iron(III)-Monoamidate Complexes as Catalysts for Methylene-Selective Oxidation of Simple Alkanes[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4453-4462.

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图/表 6

Figure 1. Selected examples of nonheme metal complexes of linear tetradentate N4 ligands used in methylene oxidation and the proposed mechanism

Scheme 1. Schematic diagram of the synthetic route for (L)-proline-derived monoamide tetradentate N4 ligands

Entry	Deviation from standard conditions	Product yield^b/%		A/K^c
Entry	Deviation from standard conditions	1a	1k	A/K^c
1	None	58	4.2	14
2	C2 instead of C1	11	2.9	3.8
3	C3 instead of C1	22	5.0	4.4
4^d	TFE instead of HFIP	57	6.7	8.5
5^d	NFTB instead of HFIP	ND	ND	ND
6	CH₃CN instead of HFIP	36	7.0	5.1
7^d	HFIPMe instead of HFIP	ND	ND	ND
8	3.0 mol% C1	60	4.6	13
9	1.0 mol% C1	44	32	14
10^d	Fe(ClO₄)₃•xH₂O instead of C1	ND	ND	ND
11	3.0 equiv. of H₂O₂	50	3.6	14
12	0.15 equiv. of HOAc	50	4.8	10
13	Without HOAc	43	3.9	11

Table 1. Optimization of reaction conditionsa

Entry	BDE_C—H^b/(kJ•mol⁻¹)	A/K^d
1	416	14
2	400	12
3	393	7.2
4	400	5.4
5	406	8.0
6	414	12
7	402	6.6
8	415	2.8
8	415
9	410	3.8
9	410
10	410	4.1
10	410
11	407	2.4
11	407	2.4

Table 2. Selective oxidation of methylenic C—H bonds of hydrocarbonsa

Figure 2. (a) CV of C1 (0.8 mmol/L) in CH3CN (scan rate=100 mV•s－1, inset: CV of C1 (0.8 mmol/L) in CH3CN at －0.2~0.4 V); (b) KIE determined in the competitive oxidation of cyclohexane and cyclohexane-d12 by C1 and H2O2

Scheme 2. Proposed mechanism for nonheme iron(III) complex-catalyzed alkane oxidation

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