Rhodium(I)-Catalyzed [2+2+1]-Carbonylative Cycloaddition of Diynes with Anthracene α-Diketone as the Source of CO

Abstract

We report on the use of anthracene α-diketone as a source of carbon monoxide (CO) in carbonylation reactions. Photoirradiation by a 5 W blue LED of a diyne in the presence of anthracene α-diketone and a rhodium(I) catalyst resulted in a [2+2+1]-carbonylative cycloaddition of the diyne to CO released from the anthracene α-diketone to give a high yield (up to 99%) of the corresponding cyclopentadienone. This is the first demonstration of a CO-gas-free carbonylation reaction using anthracene α-diketone. Light irradiation was a major factor both in the generation of CO from anthracene α-diketone and in the catalytic activity. A halogen lamp, a fluorescent lamp, or sunlight also served as a light source for this reaction. With this system, there is no need for an additional reagent for generating CO.

Key words

anthracene α-diketone - [2+2+1]-carbonylative cycloaddition - diynes - cyclopentadienes - carbon monoxide

Publication History

Received: 18 August 2022

Accepted after revision: 07 September 2022

Accepted Manuscript online:
07 September 2022

Article published online:
11 October 2022

• References and Notes


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• 19 In the presence of [Rh(cod)₂]BF₄, the reaction of diyne 2a with CO under irradiation by a 25 W fluorescent light (λ = 400 nm) led to the formation of product 3a in 69% yield.
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• 21 4,6-Diphenyl-1H-cyclopenta[c]furan-5(3H)-one; Typical ­Procedure A 5 mL two-necked flask was charged with[Rh(cod)₂]BF₄ (10.15 mg, 0.025 mmol), diyne 2a (0.50 mmol) and 1 (118.14 mg, 0.5 mmol), and anhydrous CH₂Cl₂ (5 mL) was added with stirring. The flask was subjected to three freeze–pump-thaw cycles with liquid N₂. The reaction was maintained as a closed system (internal volume: 10 mL). When the mixture reached rt, it was irradiated with a 5 W blue LED (λ = 480 nm) placed 1 cm from the reaction vessel, with both the vessel and light source covered by a box. After 9 h, the irradiation was stopped and PPh₃ (26.4 mg, 0.1 mmol; 4 equiv to Rh) was added. After 1 h, the stirring was again stopped and the reaction vessel was opened. The resulting solution was examined by TLC, transferred to a round-bottomed flask, and concentrated in vacuo. The concentrate was purified by column chromatography [silica gel, hexane–EtOAc (10:1)] to give a violet solid; yield: 125 mg (93%); mp 102–103 °C. This was accompanied by recovered anthracene in 97% yield. ¹H NMR (500 MHz, CDCl₃): δ = 7.59 (d, J = 7.0 Hz, 4 H), 7.40 (t, J = 7.0 Hz, 4 H), 7.29 (t, J = 7.0 Hz, 2 H), 4.96 (s, 4 H). ¹³C NMR (126 MHz, CDCl₃): δ = 201.5, 157.8, 131.0, 128.8, 127.8, 127.7, 117.4, 67.4. HRMS (EI): m/z [M⁺] calcd for C₁₉H₁₄O₂: 274.0994; found: 274.0991.