Bidentate Lewis Acid-Catalyzed Inverse Electron-Demand Diels–Alder Reaction of Phthalazines and Cyclooctynes

Michel Große; Hermann A. Wegner

doi:10.1055/a-2204-9522

Synlett, Inhaltsverzeichnis

Synlett 2024; 35(09): 1019-1022
DOI: 10.1055/a-2204-9522

cluster

Chemical Synthesis and Catalysis in Germany

Bidentate Lewis Acid-Catalyzed Inverse Electron-Demand Diels–Alder Reaction of Phthalazines and Cyclooctynes

Michel Große

^aInstitute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany

^bCenter of Material Research (LaMa/ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, 35392 Giessen, Germany

,

Hermann A. Wegner∗

^aInstitute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany

^bCenter of Material Research (LaMa/ZfM), Justus Liebig University, Heinrich-Buff-Ring 16, 35392 Giessen, Germany

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Abstract

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Abstract

Herein we report a method for facilitating the inverse-electron-demand Diels–Alder reaction of 1,2-diazines and cyclooctynes by utilizing a boron-based bidentate Lewis acid catalyst. Readily available electron-deficient and electron-rich phthalazines proved to be suitable substrates in this transformation. The described method enables the facile construction of diversely substituted polycyclic aromatic hydrocarbons fused to eight-membered carbocycles.

Key words

cycloaddition - diazines - cyclooctyne - bidentate catalysis - polycyclic aromatic hydrocarbons - Diels–Alder reactions

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References and Notes
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19 General procedure for the BDLA-catalyzed IEDDA reaction: In a nitrogen-filled glove box, (substituted) phthalazine 1 (0.10 mmol, 1.0 equiv) and BDLA catalyst (5.0 μmol, 5.0 mol%) were suspended in anhydrous and degassed 1,4-dioxane (1.0 mL) in a 4 mL screw-cap vial with a stirrer bar. Cyclooctyne (2) or exo-BCN (1.1–3.0 equiv) was added to the mixture, and the vial was sealed and taken out of the glove box. The mixture was stirred at the given temperature for the given time. Afterwards, the reaction mixture was concentrated in vacuo. The ratio of product to unreacted phthalazine was determined by ¹H NMR spectroscopic analysis of the crude mixture. The crude mixture was purified by column chromatography (3 g of silica gel) to afford product 3 or 4
20 ((1r,1aR,11aS)-1a,2,3,10,11,11a-hexahydro-1H-cyclopropa[5,6]cycloocta[1,2-b]naphthalen-1-yl)methanol (4a): Yield: 13 mg (52%); colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.76–7.71 (m, 2 H), 7.56 (s, 2 H), 7.41–7.36 (m, 2 H), 3.38 (d, J = 6.5 Hz, 2 H), 3.10 (ddd, J = 14.1, 8.3, 5.7 Hz, 2 H), 2.92 (dt, J = 14.1, 5.8 Hz, 2 H), 2.59–2.45 (m, 2 H), 1.42–1.25 (m, 3 H), 0.77–0.66 (m, 3 H) ppm. ¹³C NMR (101 MHz, CDCl₃): δ = 141.21 (2 C), 132.49 (2 C), 128.04 (2 C), 127.08 (2 C), 125.24 (2 C), 66.78, 33.63 (2 C), 30.16 (2 C), 29.76 (2 C), 22.03. HRMS (ESI): m/z calcd for C₁₈H₂₀ONa: 275.1406 [M + Na]⁺; found: 275.1406.

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