Synthesis of New Chiral Diaryliodonium Salts

Dedicated to Prof. Dr. Peter Vollhardt

Abstract

A structurally diverse range of chiral diaryliodonium salts have been synthesised which have potential application in metal-free stereoselective arylation reactions.

Key words

arylation - diaryliodonium salts - hypervalent iodine - stereoselective synthesis

• References and Notes

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• 27 (R)-(2′-Phenoxy-1,1′-binaphthyl-2-yl)(phenyl)iodonium Tetrafluoroborate (7a) To a solution of (R)-2-(diacetoxy)iodo-2′-phenoxy-1,1′-binaphthyl (14a, 107 mg, 0.18 mmol) in CH₂Cl₂ (4 mL) at –78 °C was added dropwise BF₃·OEt₂ (57 μL, 0.45 mmol). After 2 min, PhB(OH)₂ (24 mg, 0.20 mmol) was added in one portion. The reaction was allowed to warm to r.t. and stirred for 15 min at r.t. The crude reaction mixture was applied to a short silica plug (1.6 g). Unreacted starting material and impurities were eluted with CH₂Cl₂ (20 mL). The iodonium salt was eluted using with 5% MeOH in CH₂Cl₂ (15 mL). This fraction was concentrated under vacuum. Subsequent precipitation with MeOH–Et₂O yielded 7a (91 mg, 79%) as a light brown solid; mp 164.5–166 °C; [α]_D ²⁰ 74.0 (c 1.0, CHCl₃). IR (neat): 3061, 2363, 1489, 1235, 1053, 733 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 8.51 (1 H, d, J = 9 Hz), 8.20 (2 H, d, J = 9 Hz), 8.09 (1 H, d, J = 8 Hz), 8.00 (1 H, d, J = 8 Hz), 7.65 (1 H, t, J = 8 Hz), 7.45–7.32 (7 H, m), 7.22 (2 H, t, J = 8 Hz), 7.11 (2 H, t, J = 8 Hz), 7.04–6.98 (2 H, m), 6.83–6.80 (2 H, m), 6.46 (1 H, d, J = 9 Hz) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 156.0, 152.5, 141.8, 140.5, 135.1, 134.9, 133.2 (2 C), 132.0, 131.9 (2 C), 131.5, 131.1, 130.1, 129.5, 129.0, 128.3, 128.2, 128.1, 127.7, 127.1, 126.2, 125.1, 124.1, 124.0, 123.7, 118.8 (2 C), 118.2, 118.0, 112.6, 98.0 ppm. ¹⁹F NMR (282 MHz, CDCl₃): δ = –154.6 (4 F) ppm. MS (APCI⁺): m/z = 549 (100) [M⁺]. HRMS (ES⁺): m/z calcd for C₃₂H₂₂IO [M]⁺: 549.0710; found: 549.0699.
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• 32 (R)-(2′-Iodo-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-yl)(phenyl)iodonium Tetrafluoroborate (8) To a solution of (R)-2,2′-diiodo-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl (17, 210 mg, 0.41 mmol) in MeCN (6 mL) and AcOH (2 mL) was added Selectfluor (868 mg, 2.45 mmol). The reaction was stirred at r.t. for 9 h then concentrated under vacuum. H₂O (5 mL) was added, and the product extracted with CH₂Cl₂ (2 × 15 mL). Combined organic extracts were washed with H₂O (5 mL) and brine (5 mL) and concentrated under vacuum to give 18 (264 mg, 86%) as a yellow oil. ¹H NMR analysis showed the presence of a broad acetate signal (δ = 1.75 ppm) with integration consistent with 18. This crude material was promptly dissolved in CH₂Cl₂ (4 mL) and cooled to –78 °C. BF₃·OEt₂ (223 μL, 1.76 mmol) was added dropwise, followed after 2 min by PhB(OH)₂ (45 mg, 0.37 mmol) in one portion. The reaction was allowed to warm to r.t. and stirred for 15 min. The crude reaction mixture was applied to a short silica plug (2 g). Unreacted starting material and impurities were eluted with hexane–CH₂Cl₂ (1:0 → 0:1). The iodonium salt was eluted using with 10% MeOH in CH₂Cl₂ (10 mL). Subsequent precipitation with CH₂Cl₂–Et₂O yielded 19 (135 mg, 65%) as a colourless solid, mp 116–118 °C; [α]_D ²⁰ –85.0 (c 1.0, CHCl₃). IR (neat): 2940, 1443, 1267, 1051, 729, 700 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 7.84 (2 H, d, J = 8 Hz), 7.70 (1 H, d, J = 8 Hz), 7.67 (1 H, d, J = 8 Hz), 7.59 (1 H, t, J = 7 Hz), 7.41 (2 H, t, J = 8 Hz), 7.19 (1 H, d, J = 8 Hz), 6.96 (1 H, d, J = 8 Hz), 2.92–2.76 (4 H, m), 2.34–2.26 (1 H, m), 2.13–2.00 (2 H, m), 1.92–1.84 (1 H, m), 1.80–1.67 (8 H, m) ppm. ¹³C NMR (125 MHz, MeOD-d ₄): δ = 148.1, 146.3, 144.5, 140.6 (2 C), 138.8, 138.0, 137.4 (2 C), 135.7, 134.1, 133.7, 133.4, 133.2 (2 C), 115.1, 113.2, 98.2, 30.8, 30.4, 29.9, 29.6, 23.8 (2 C), 23.2, 23.1 ppm. ¹⁹F NMR (282 MHz, CDCl₃): δ = –149.0 (4 F) ppm. MS (EI⁺): m/z = 591 (100) [M⁺]. HRMS (APCI⁺): m/z calcd for C₂₆H₂₅I₂ [M]⁺: 591.0046; found: 591.0051.