Synthesis of Functionalized Biaryls Based on a Heck Cross-Coupling-[3+3] Cyclization Strategy

Abstract

6-Arylsalicylates were regioselectively prepared by formal [3+3] cyclization of 1,3-bis(silyloxy)-1,3-butadienes with 1-aryl-3-ethoxyprop-2-en-1-ones which are available by Heck reaction of benzoyl chlorides with ethylvinyl ether. In this context, the first [3+3] cyclizations of brominated substrates are reported.

arenes - cyclizations - regioselectivity - silyl enol ethers

References and Notes

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Typical Procedure for the Heck Reaction of Ethylvinyl Ether with Acid Chlorides
To a mixture of ethylvinyl ether (2.90 g, 40.0 mmol) and of Et₃N (1.20 g, 12.0 mmol) in a pressure tube was added Pd(OAc)₂ (20 mg, 0.1 mmol) under Ar atmosphere. The mixture was stirred until a clear yellow solution was formed. To the mixture were added benzoylchloride (1.20 g, 10.0 mmol), and the mixture was stirred at 80 °C for 24 h. The mixture was poured into Et₂O (50 mL) and the solid (triethylammonium hydochloride) was filtered off. The filtrate was concentrated under reduced pressure and the residue was purified by chromatography (SiO₂, heptanes-EtOAc = 10:1 → 5:1) to give 3a as a slightly yellow oil (3.80 g, 55%).

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General Procedure for the Synthesis of Salicylates 5 To a CH₂Cl₂ solution (1 mL) of 3a (176 mg, 1.0 mmol) and 4a (260 mg, 1.0 mmol) was added a CH₂Cl₂ solution (1 mL) of TiCl₄ (0.12 mL, 1.0 mmol) at -78 °C. The temperature of the solution was allowed to warm to 20 °C within 14 h. To the mixture was added CH₂Cl₂ (10 mL) and HCl (10 mL, 10%). The organic and the aqueous layer were separated and the latter was extracted with CH₂Cl₂. The combined organic layers were dried (Na₂SO₄), filtered, and the filtrate was concentrated in vacuo. The residue was purified by chromatography (heptane-EtOAc, 10:1) to give 5a as a slightly yellow oil (0.081 g, 36%).
Methyl 6-phenylsalicylate (5a): ¹H NMR (300 MHz, CDCl₃): δ = 3.47 (s, 3 H, OCH₃), 6.80 (d, ³ J = 7.4 Hz, 1 H, CH), 6.99 (d, ³ J = 7.4 Hz, 1 H, CH), 7.20-7.43 (m, 6 H, CH), 10.60 (s, 1 H, OH). ¹³C NMR (50.3 MHz, CDCl₃): δ = 52.1 (OCH₃), 112.5 (CH_Ph/Ar), 117.0, 123.0, 127.3, 128.0, 128.5, 134.1, 143.1, 145.3, 161.7, 171.8 (CO). IR (neat) = 3060 (m), 2952 (m), 1667 (s), 1601 (s), 1572 (m), 1501 (w), 1439 (s), 1343 (m), 1271 (s), 1220 (s) cm^-1. MS (EI, 70 eV): m/z (%) = 228 (36) [M⁺], 196 (100), 168 (53), 139 (34). ESI-HRMS: m/z calcd for C₁₄H₁₂O₃ [M + 1]⁺: 228.07864; found: 228.07866.

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CCDC-679813 and CCDC-679814 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.