Transition-Metal-Free Synthesis of 3-Ethynylcoumarins by a DBU-Promoted Intramolecular Morita–Baylis–Hillman-Type Reaction/Dehydration/Isomerization Cascade

Shuolu Dai; Xiaoyu Gu; Zhen Wang; Weijun Yao

doi:10.1055/a-1938-0643

Synlett, Inhaltsverzeichnis

Synlett 2022; 33(20): 2009-2012
DOI: 10.1055/a-1938-0643

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Transition-Metal-Free Synthesis of 3-Ethynylcoumarins by a DBU-Promoted Intramolecular Morita–Baylis–Hillman-Type Reaction/Dehydration/Isomerization Cascade

Shuolu Dai‡

^aDepartment of Chemistry, Zhejiang Sci-Tech University, Hangzhou, 310018, P. R. of China

,

Xiaoyu Gu‡

^aDepartment of Chemistry, Zhejiang Sci-Tech University, Hangzhou, 310018, P. R. of China

,

Zhen Wang∗

^bSchool of Pharmaceutical Sciences and Chongqing Key Laboratory of Natural Drug Research, Chongqing University, Chongqing, 401331, P. R. of China

,

Weijun Yao ∗

^aDepartment of Chemistry, Zhejiang Sci-Tech University, Hangzhou, 310018, P. R. of China

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Abstract

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Abstract

A transition-metal-free synthesis of 3-ethynylcoumarins from salicylaldehyde-derived alkynoates was developed involving a DBU-promoted intramolecular Morita–Baylis–Hillman-type reaction/dehydration/isomerization cascade. A wide variety of alkynoates were employed to deliver 3-ethynylcoumarins in moderate to good yields.

Key words

transition-metal-free reaction - ethynylcoumarins - Morita–Baylis–Hillman reaction - step economy - cascade reaction

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Referenzen

References and Notes

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11 3-Ethynylcoumarins 3a–p; General Procedure DBU (0.6 mmol, 90 μL) was added to a suspension of the appropriate 2-formylphenylbutynoate 2 (0.5 mmol) and 4 Å MS (100 mg) in anhydrous (CH₂Cl)₂ (10 mL) under N₂ in a dry Schlenk tube at r.t., and the resulting mixture was stirred at r.t. until the substrate was fully consumed (TLC, ~0.5 h). The mixture was filtered and the filter was washed with CH₂Cl₂. The filtrate was concentrated, and the residue was purified by flash column chromatography (silica gel, PE–EtOAc). 3-Ethynyl-7-methyl-2H-chromen-2-one (3b) White solid; yield: 47.9 mg (52%); mp 182.0–186.3 °C. IR (KBr): 3235, 3045, 2926, 2101, 1721, 1616, 1604, 1423 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.90 (s, 1 H), 7.35 (d, J = 7.8 Hz, 1 H), 7.12 (s, 1 H), 7.11 (d, J = 8.5 Hz, 1 H), 3.34 (s, 1 H), 2.45 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 159.6, 153.6, 146.6, 144.3, 127.5, 126.1, 117.0, 116.1, 110.6, 83.2, 77.4, 21.9. HRMS (ESI): m/z [M+H]⁺ calcd for C₁₂H₉O₂: 185.0597; found: 185.0604.
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