The synthesis of tetracyclic coumarins via decarboxylative asymmetric [4+2] cycloadditions enabled by Pd(0)/Cu(I) synergistic catalysis

doi:10.1016/S1872-2067(21)64051-2

Abstract

Abstract:

Tetracyclic coumarins are a class of important compounds with diverse and superior pharmacological activities. However, a direct stereoselective method from simple and readily-made coumarins derivatives remains challenging due to the inertness of coumarins as dienophiles. Herein, we develop a decarboxylative asymmetric [4+2] cycloaddition of 3-cyanocoumarins with vinyl benzoxazinones, affording the coumarin-derived condensed rings bearing three continuous stereocenters in high yields with excellent diastereoselectivities (>20/1 d.r.) and enantioselectivities (up to 99% ee). This direct enantioselective reaction was achieved by a Pd(0)/Cu(I) bimetallic catalytic system. The mechanism studies indicated that the synergistic activation effect, in which chiral Cu(I) as an available Lewis acid catalyst activates 3-cyanocoumarin and chiral Pd(0) complex activates benzoxazinone by the formation of π-allyl-palladium intermediate, plays an important role on the stereoselective control. The current work provides a new activation modes of Cu catalyst in the Pd/Cu bimetallic catalytic system.

Key words: Synergistic catalysis, Pd(0)/Cu(I) catalysis, Asymmetric catalysis, [4+2] Cycloaddition, Tetracyclic coumarins, Chiral catalysis

Kai Wang, Xiangfeng Lin, Qian Li, Yan Liu, Can Li. The synthesis of tetracyclic coumarins via decarboxylative asymmetric [4+2] cycloadditions enabled by Pd(0)/Cu(I) synergistic catalysis[J]. Chinese Journal of Catalysis, 2022, 43(7): 1812-1817.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64051-2

https://www.cjcatal.com/EN/Y2022/V43/I7/1812

Figures/Tables 6

Scheme 1. Asymmetric synthesis of tetracyclic coumarins and our strategy.

Table 1 Optimization of reaction conditions a.


Entry	Change from standard condition	Yield (%) ^b	d.r. ^c	ee (%) ^d
1	none	74	>20:1	95
2	without Pd catalyst	0	—	—
3	without Cu catalyst	64	>20:1	67
4	A1 instead of A2	66	>20:1	65
5	A3 instead of A2	10	>20:1	76
6	A4 instead of A2	50	>20:1	97
7	A5 instead of A2	53	>20:1	80
8	A11 instead of A2	51	>20:1	43
9	A12 instead of A2	46	>20:1	67
10	B1 instead of B5	65	>20:1	93
11	B2 instead of B5	61	>20:1	85
12	B3 instead of B5	54	>20:1	69
13	B4 instead of B5	56	>20:1	95
14	ent-B5 instead of B5	41	>20:1	78

Scheme 2. Scope of 3-cyanocoumarins. Reaction conditions: 1a (0.10 mmol), 2 (3.0 equiv), Pd2(dba)3·CHCl3 (5 mol%), A2 (12 mol%), Cu(OTf) (5 mol%), B5 (6 mol%), rt, MeCN/DMF = 1:1 (1 mL), 6 h. Yields were for the isolated products after column chromatography. The ee values were determined by chiral HPLC.

Scheme 3. Scope of vinyl benzoxazinones. Reaction conditions: 1 (0.10 mmol), 2a (1.5 equiv), Pd2(dba)3·CHCl3 (5 mol%), A1 (12 mol%), CuTc (10 mol%), B4 (12 mol%), rt, MeCN/o-xylene = 1:1 (1 mL), 6 h. Yields were for the isolated products after column chromatography. The ee values were determined by chiral HPLC.

Scheme 4. Mechanistic investigations.

Scheme 5. Synthetic transformations.

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