纯水及空气中芳香羧酸和丙烯酸酯氧化偶联构筑苯酞的绿色方法

doi:10.6023/cjoc202208034

摘要/Abstract

苯酞是一类重要的杂环化合物, 广泛存在于药物和天然产物中, 其合成备受关注. 本研究发展了一种水促进、铑催化芳香酸和丙烯酸酯通过[3+2]串联环化反应构筑苯酞的绿色方法, 反应在空气和纯水介质中进行, 无需任何添加剂. 与文献相比, 该方法具有反应条件方便、操作简单、无添加剂等特点. 机理研究表明, 催化循环中, 除了外部氧化剂氧化Rh(I)外, 还包含丙烯酸酯作为氢受体的氢转移过程使活性Rh(III)再生, 这一机理与文献报道的金属催化苯酞的合成机理不同. 利用该方法, 可一步合成具有生物活性的(4-羟基-3-氧亚基-1,3-二氢异苯并呋喃-1-基)乙酸.

关键词: 水相反应, 串联环化, 氧化偶联, 苯酞

Phthalides represent an important class of bioactive heterocycle extensively found in pharmaceuticals and natural products, their syntheses have attracted extensively attention. A water-promoted and rhodium-catalyzed [3+2] tandem cyclization of aromatic acids and acrylates has been developed in air and neat water free of any additives, which provides an environmentally benign approach for constructing phthalide motifs. Compared with previous literatures, this methodology features quite simple reaction conditions, simple operation and additive-free. Mechanistic studies indicate that apart from the many other well-known oxidations of Rh(I) by external oxidant, hydrogen transfer with the acrylate being a hydrogen acceptor is involved to regenerate the active Rh species, which is different from documented metal-catalyzed phthalides syntheses. The application of this protocol is further demonstrated by the green synthesis of biologically active isoochracinic acid in one step.

Key words: on water reaction, tandem cyclization, oxidative coupling, phthalides

引用此文

魏文婷, 李壮壮, 李婉迪, 李嘉琪, 石先莹. 纯水及空气中芳香羧酸和丙烯酸酯氧化偶联构筑苯酞的绿色方法[J]. 有机化学, 2023, 43(3): 1177-1186.

Wenting Wei, Zhuangzhuang Li, Wandi Li, Jiaqi Li, Xianying Shi. Green Method for Constructing Phthalides via Oxidative Coupling of Aromatic Acids and Acrylates in Neat Water and Air[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1177-1186.

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图/表 7

Figure 1. Representative examples with phthalide scaffold

Scheme 1. Catalytic reactions between aromatic acids and acrylates

Entry	Solvent	Yield^b/%
1	H₂O	84
2	—	ND^c
3	CH₃OH	6
4	HFIP	13
5	Acetone	12
6	DMF	17
7	EtOH	ND
8	DCE	ND
9	EtOAc	ND
10	DME	ND
11	TFE	ND
12	CH₃CN	ND
13	THF	ND
14	Dioxane	ND
15	PhCH₃	ND
16	PhCl	ND

Table 1. Selected results for optimizing reaction conditionsa

Table 2. Substrate scope for tandem cyclization reactiona

Scheme 2. Synthesis of isoochracinic acid

Scheme 3. Mechanistic studies

Scheme 4. Plausible reaction mechanism

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