Green Method for Constructing Phthalides via Oxidative Coupling of Aromatic Acids and Acrylates in Neat Water and Air

doi:10.6023/cjoc202208034

Abstract

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

Cite this article

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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Fig. & Tab. 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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