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

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

Publication History

Received: 31 August 2021

Accepted after revision: 20 October 2021

Article published online:
18 February 2022

• References and Notes

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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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• 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⁺].
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