Functionalized Hydroxyquinones through Suzuki-Type Coupling of Phenyliodonium Ylides of Hydroxyquinones with Arylboronic Acids

Abstract

The palladium(II) acetate catalyzed reaction of phenyl­iodonium ylides of 2-hydroxyquinones with arylboronic acids affords a variety of 3-substituted 2-hydroxyquinone derivatives. Best yields are obtained by using tri(tert-butyl)phosphine as a ligand.

Key words

hydroxyquinones - phenyliodonium ylides - Suzuki coupling - palladium-catalyzed - boronic acids

References and Notes

• 1 Thomson RH. Naturally Occurring Quinones IV   Blackie Academic & Professional; London: 1997. 
• 2 Spyroudis S. Molecules  2000,  5:  1291 
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• 7a Transylidation reactions of zwitterionic iodonium compounds are well known, see: Varvoglis A. In The Organic Chemistry of Polycoordinated Iodine   VCH; New York: 1992. 
• 7b

  In our case the side-reaction with phosphines is described in Scheme [2] .

• 9 For a recent review on Suzuki coupling reactions in water, see: Leadbeater NE. Chem. Commun.  2005,  2881 
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8

Coupling Reaction of Ylides 5 and 9 with Arylboronic Acids 6; General Procedure. A degassed solution of arylboronic acid (1.1 mmol) and P(t-Bu)₃ (0.1 mmol) in DME-H₂O (4:1, 10 mL) was added to a degassed flask containing a mixture of ylide 5 or 9 (0.5 mmol), LiOH·H₂O (2.7 mmol), and Pd(OAc)₂ (6 mg, 4 mmol%) and the resulting suspension was stirred at r.t. under Ar for 5 h. The solution was acidified to pH 6 by the addition of 4-5 drops of acetic acid and excess DME was evaporated. CH₂Cl₂ (10 mL) was added and the suspension was filtered through filter paper, which was moistened with CH₂Cl₂ (1-2 mL). The filtrate was dried, concentrated, and subjected to column chromatography (silica gel, hexanes-EtOAc, 3:1) to afford the coupling products 7 and 10. 2-Hydroxy-3-(3-thienyl)-1,4-naphthoquinone ( 7a): Mp 126-127 °C. IR (KBr): 3322, 1650, 1590 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 8.16 (1 H, d, J = 8.0 Hz), 8.10 (1 H, br s), 8.08 (1 H, d, J = 8.0 Hz), 7.94 (1 H, s), 7.80-7.65 (3 H, m), 7.35 (1 H, d, J = 4.8 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 183.8, 181.6, 151.5, 135.2, 133.1, 130.0, 129.7, 129.5, 129.1, 127.3, 126.0, 124.0, 123.2, 116.9. MS (EI): m/z (%) = 256 (100) [M⁺], 228 (68), 184 (25), 171 (71). Anal. Calcd for C₁₄H₈O₃S: C, 65.61; H, 3.15. Found: C, 65.37; H, 3.19.

10

The coupling reaction was repeated exactly under the previously described conditions, using 1 mmol of iodobenzene instead of ylide 5