介孔ETS-10沸石担载Pd高效催化内炔氧化制备1,2-二酮

doi:10.6023/cjoc202301016

摘要/Abstract

使用担载Pd的介孔ETS-10 (Pd/METS-10)催化剂在清洁的反应条件下, 实现了内炔氧化合成1,2-二酮类衍生物. 研究发现, 催化剂上高分散的Pd(II)和炔烃配位形成电子受体供体复合物(EDX)是反应顺利进行的关键. 随后二甲基亚砜(DMSO)亲核进攻生成的EDX, 相继发生加成和消除反应, 从而生成目的产物. Pd/METS-10催化的内炔氧化反应具有优异的产物选择性和好的底物范围, 能够同时兼容对称/不对称内炔, 且对底物的电子性质和立体效应不敏感. 此外, Pd/METS-10催化剂在反应中表现出优异的重复性能, 在循环使用5次后没有明显的活性损失. 最后, 根据表征结果和控制实验结果, 提出了Pd/METS-10催化的内炔氧化制备1,2-二酮的反应机理.

关键词: Pd/METS-10, 内炔, 1,2-二酮类衍生物, 电子供体受体复合物, 氧化反应

The 1,2-dione compounds was synthesized under clean reaction conditions over Pd/METS-10 catalyst. It has been found that the key step of the protocol is forming an electron donor-acceptor complex (EDX), as the coordination of Pd(II) and alkynyl. Then the nucleophilic addition and elimination reactions of dimethyl sulfoxide (DMSO) to the EDX were occurred, affording the target product. Pd/METS-10 catalyzed endo-acetylene oxidation possesses excellent product selectivity and good substrate scope. It is compatible with both symmetric and asymmetric endo-acetylene and is insensitive to the electronic properties and stereoscopic effects of the substrate. In addition, Pd/METS-10 catalyst showed excellent repetition performance in the reaction, with no significant loss of activity after five cycles. Finally, according to the characterization and control experiment results, the reaction mechanism of Pd/METS-10 catalyzed acetylene oxidation to produce 1,2-dione was proposed.

Key words: Pd/METS-10, internal alkyne, 1,2-diketone compound, electron donor-acceptor complex, oxidation reaction

引用此文

刘长俊, 胡慧玲, 刘宬宏, 朱超杰, 唐天地. 介孔ETS-10沸石担载Pd高效催化内炔氧化制备1,2-二酮[J]. 有机化学, 2023, 43(8): 2953-2960.

Changjun Liu, Huiling Hu, Chenghong Liu, Chaojie Zhu, Tiandi Tang. Pd Supported on Mesoporous ETS-10 Zeolite Catalyst with Superior Catalytic Performances in Synthesizing 1,2-Diones from the Oxidation of Internal Alkynes[J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2953-2960.

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图/表 9

图1. 含有1,2-二酮结构单元的一些重要生物碱

Figure 1. Some important bioactive bases containing 1,2-di- ketone structural units

图式1. 1,2-二酮类化合物合成的一些方案

Scheme 1. Some protocols for synthesis of 1,2-dione com- pounds

图2. METS-10和Pd/METS-10样品的(a) XRD谱图、(b) N2吸-脱附曲线、(c)孔径分布图和(d)样品Pd/METS-10的XPS拟合谱图曲线

Figure 2. XRD spectra (a), N2 adsorption-desorption curves (b), pore size distribution (c) of METS-10 and Pd/METS-10 samples, and XPS fitting spectrum of Pd/METS-10 sample (d)

Entry	Catalyst	Solvent	Temp./℃	Yield^b/%
1	None	DMSO	150	n.d.^c
2	METS-10	DMSO	150	n.d.
3	Pd(NO₃)₂^d	DMSO	150	41
4	Pd(OAc)₂^d	DMSO	150	37
5	Pd/METS-10	DMSO	150	92
6	Pd/METS-10	DMSO	150	91^e
7	Pd/METS-10	Benzene	150	n.d.
8	Pd/METS-10	Cycloethane	150	n.d.
9	Pd/METS-10	1,4-Dioxane	150	n.d.
10	Pd/METS-10	DMF	150	n.d.
11	Pd/METS-10	NMP	150	n.d.
12	Pd/METS-10	DMSO	130	57
13	Pd/METS-10	DMSO	110	30

表1. 反应条件优化a

Table 1. Reaction condition optimization

表2. 内炔氧化反应的底物范围a

Table 2. Substrate scope of oxidation of internal alkynes

表3. 邻苯二胺和1,2-二酮合成喹喔啉类化合物的合成a

Table 3. Synthesis of quinoxalines from o-phenylenediamines and 1,2-diketones

图式2. 二苯基乙炔氧化为1,2-二酮反应的控制实验

Scheme 2. The control experiments of the oxidization of diphenylacetylene to 1,2-diketone

图式3. Pd/ETS-10催化1,2-二芳基内炔氧化反应的可能机理

Scheme 3. Possible mechanism of Pd/ETS-10 catalyzed oxidation of 1,2-diaryl alkynes

图3. Pd/METS-10催化剂在二苯乙炔氧化反应中的循环实验

Figure 3. Cyclic experiment of Pd/METS-10 catalyst in diphenylacetylene oxidation reaction

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