Complementary Photocatalytic Toolbox: Control of Intramolecular endo- versus exo-trig Cyclizations of α-Phenyl Olefins to Oxaheterocyclic Products

Fabian Weick; Desirée Steuernagel; Arina Belov; Hans-Achim Wagenknecht

doi:10.1055/s-0040-1719871

Synlett, Inhaltsverzeichnis

CC BY-NC-ND 4.0 · Synlett 2022; 33(12): 1199-1204
DOI: 10.1055/s-0040-1719871

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Organic Photoredox Catalysis in Synthesis – Honoring Prof. Shunichi Fukuzumi’s 70th Birthday

Complementary Photocatalytic Toolbox: Control of Intramolecular endo- versus exo-trig Cyclizations of α-Phenyl Olefins to Oxaheterocyclic Products

Authors

Fabian Weick
Desirée Steuernagel
Arina Belov
Hans-Achim Wagenknecht ∗

Abstract

Alle Artikel dieser Rubrik

Dedicated to Shunichi Fukuzumi on his 70^th birthday.

Abstract

The regioselectivity of the intramolecular cyclization of bifunctional α-phenyl alkenes can be controlled simply by the choice of the organic chromophore as the photocatalyst. The central photoredox catalytic reaction in both cases is a nucleophilic addition of the hydroxy function to the olefin function of the substrates. N,N-(4-Diisobutylaminophenyl)phenothiazine catalyzes exo-trig cyclizations, whereas 1,7-dicyanoperylene-3,4,9,10-tetracarboxylic acid bisimides catalyze endo-trig additions to products with anti-Markovnikov regioselectivity. We preliminarily report the photoredox catalytic conversions of 11 representative substrates into 20 oxaheterocycles in order to demonstrate the similarity, but also the complementarity, of these two variants in this photoredox catalytic toolbox.

Key words

photochemistry - photocatalysis - perylene bisimide - phenothiazine - nucleophilic addition - cyclization

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References and Notes

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24 1,7-Dibromoperylene-3,4,9,10-tetracarboxylic Acid Bisimides 13a–j; General Procedure The appropriate amine RNH₂ (5.46 mmol, 3.00 equiv) was added to a solution of dibromide 12 (1.82 mmol, 1.00 equiv) in DMF (13a–f) or propionic acid (13e–j), and the mixture heated to 80 °C (13a–f in DMF) or under reflux (13g–j in propionic acid) for 15 h. In the case of 13i and 13j, ZnOAc (0.87 mmol, 0.04 equiv) was added. The solution was then cooled to r.t. and poured into H₂O. The resulting precipitate was collected by filtration and washed with H₂O. The crude product was purified by column chromatography (silica gel, CH₂Cl₂) to give a red solid; yield: 0.32–0.65 mmol (18–36%).
25 13j Red solid; yield: 0.32–0.65 mmol (31%) R_f = 0.7. ¹H NMR (500 MHz, CDCl₃): δ = 9.57 (d, J = 8.1 Hz, 2 H), 9.03 (s, 2 H), 8.81 (d, J = 8.1 Hz, 2 H), 7.52 (t, J = 7.8 Hz, 2 H), 7.37 (d, J = 7.8 Hz, 6 H), 2.84–2.54 (m, 4 H), 1.19 (d, J = 6.8 Hz, 24 H). ¹³C NMR (126 MHz, CDCl₃): δ = 163.14, 162.64, 145.73, 138.62, 133.58, 133.41, 130.79, 130.25, 130.05, 129.77, 128.86, 127.83, 124.35, 123.32, 122.99, 121.20, 29.43, 24.18. HRMS (ESI): m/z [M⁺] calcd for C₄₈H₄₀Br₂N₂O₄: 866.1355; found: 867.1431 [MH⁺].
26 Böhm A, Arms H, Henning G, Blaschka P. DE 19547209, 1997
27 1,7-Dicyanoperylene-3,4,9,10-tetracarboxylic Acid Bisimides 14a–j; General Procedure A suspension of the appropriate dibromo compound 13a–j (0.76 mmol, 1.00 equiv), Zn(CN)₂ (7.55 mmol, 10.0 equiv), dppf (0.23 mmol, 0.30 equiv), and Pd₂(dba)₃ (0.23 mmol, 0.30 equiv) in anhyd 1,4-dioxane (40 mL) was refluxed under argon for 24 h. When the reaction was complete, the mixture was cooled to r.t. and filtered. The solvent was removed under reduced pressure, and the crude product was purified by column chromatography (silica gel, CH₂Cl₂) to afford a red solid; yield: 0.34–0.53 mmol (37–71%).

14j Red solid; yield: 0.34–0.53 mmol (65%); R_f = 0.2. ¹H NMR (500 MHz, CDCl₃): δ = 9.75 (d, J = 7.9 Hz, 2 H), 9.08 (s, 2 H), 9.03 (d, J = 8.1 Hz, 2 H), 7.54 (t, J = 8.3 Hz, 2 H), 7.38 (d, J = 7.8 Hz, 4 H), 2.82–2.58 (m, 4 H), 1.19 (d, J = 6.9, 2.0 Hz, 24 H). ¹³C NMR (126 MHz, CDCl₃): δ = 162.77, 162.37, 161.93, 145.63, 138.56, 136.66, 134.17, 132.65, 132.08, 130.33, 129.71, 129.17, 127.39, 124.96, 124.48, 124.02, 119.11, 108.94, 29.52, 24.16. HRMS (ESI): m/z [M⁺] calcd for C₅₀H₄₀N₄O₄: 760.3050; found: 760.3147 [MH⁺]. Samples of 14a–i contained small amounts of the corresponding 1,6-regioisomers, detectable by NMR spectroscopy, which could not be separated, but had almost the same optical and redox properties. See also:

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29 Determination of the Solubilities of 14a–j; General ProcedureThe extinction coefficients of 13a–j were determined. The solubilities of the perylene bisimides were determined by preparing saturated solutions of them in pure MeCN at 25 °C. The solutions were filtered and their absorption was measured directly, or after further dilution when the optical density in the cuvette exceeded 1. The absorption spectroscopy was performed by using a Perkin Lambda 750 spectrometer with PTP 6 + 6 Peltier system and a Haake thermostat F4391 with 1 cm quartz-glass cuvettes (Starna) filled with a total volume of 1 mL.
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31 Photochemical Reaction; General Procedure Irradiation of the photochemical reaction was carried out in a setup designed and manufactured by the University of Regensburg and the workshop of the Institute for Physical Chemistry at KIT; this was equipped with a Nichia NVSU233A LED and an Osram Oslon SSL 150 SMD LED. The reaction samples were irradiated from the bottom. The temperature of 35 °C was controlled by a thermostat (LAUDA Alpha R8). The appropriate hydroxy alkene and photoredox catalyst were suspended in MeCN, and the mixture was degassed four by four freeze–pump–thaw cycles then stirred at 35 °C for 48 or 65 h under an inert atmosphere with irradiation at 365 or 525 nm. The mixture was cooled to r.t. then purified and analyzed (see SI).
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34 3-(2-Isopropenylphenyl)propan-1-ol (22); Typical Procedure 1-Bromo-2-isopropenylbenzene (3.49 g, 20 mmol, 1.0 equiv) was dissolved in dry THF (56 mL) under Ar, and the solution was cooled to –78 °C. A 1.6 M soln of BuLi in hexane (14 mL, 22 mmol, 1 equiv) was added dropwise over 15 min, and the mixture was stirred for 1.5 h at –78 °C. Oxetane (1.68 mL, 30 mmol, 1.5 equiv) was added dropwise to the mixture, and the mixture was stirred for 0.5 h at –78 °C, then warmed to r.t. The reaction was quenched with sat. aq NH₄Cl (25 mL) and the mixture was extracted with Et₂O. The collected organic layer was dried (Na₂SO₄) and concentrated, and the residue was purified by column chromatography [silica gel, hexane–EtOAc (4:1)] to give a colorless oil; yield: 1.53 g (17%).¹H NMR (400 MHz, CDCl₃): δ = 7.24 – 7.04 (m, 4 H), 5.19 (s, 1 H), 4.85 (s, 1 H), 3.67 (q, J = 6.1 Hz, 2 H), 2.76 – 2.67 (m, 2 H), 2.05 (s, 3 H), 1.92 – 1.80 (m, 2 H), 1.30 (t, J = 5.5 Hz, 1 H).¹³C NMR (101 MHz, CDCl₃): δ = 146.00, 143.87, 138.43, 129.23, 128.38, 127.14, 125.90, 115.03, 62.71, 34.69, 29.21, 25.39. HRMS (ESI): m/z [M⁺] calcd for C₁₂H₁₆O = 176.1201; found = 159.1166 [M – OH]⁺.
35 Methyl 4-(1-Hydroxypent-4-en-1-yl)benzoate; Typical Procedure[4-(Methoxycarbonyl)phenyl]boronic acid (1.48 g, 12.0 mmol, 1.2 equiv), pent-4-yn-1-ol (0.93 mL, 10.0 mmol, 1.0 equiv.), Pd(PPh₃)₄ (347 mg, 0.30 mmol, 3 mol%), AcOH (0.11 mL, 2.00 mmol, 0.2 equiv), and anhyd 1,4-dioxane (30 mL) were stirred at 80 °C for 24 h. Purification by flash chromatography [silica gel, hexane–EtOAc (4:1)] gave a colorless solid; yield: 810 mg (4.99 mmol, 49%). ¹H NMR (400 MHz, CDCl₃): δ = 7.99 (d, J = 8.5 Hz, 2 H), 7.47 (d, J = 8.5 Hz, 2 H), 5.39 (s, 1 H), 5.19 (s, 1 H), 3.91 (s, 3 H), 3.67 (t, J = 6.2 Hz, 2 H), 2.62 (t, J = 7.9 Hz, 2 H), 1.86–1.64 (m, 2 H), 1.34 (br s, 1 H). ¹³C NMR (101 MHz, CDCl₃) δ = 167.07, 147.34, 145.77, 129.83, 129.19, 126.22, 114.57, 62.42, 52.22, 31.49, 31.22. HRMS (ESI): m/z [M⁺] calcd for C₁₃H₁₆O₃ = 220.1099; found = 221.1168 [MH⁺].
36 E _red1(14j/14j ^∙–) = –0.15 V (vs. SCE); E ₀₀ = 2.3 eV.
37 Hansch C, Leo A, Taft RW. Chem. Rev. 1991; 91: 165

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