Development of 3,5-Di-tert-butylphenol as a Model Substrate for Biomimetic Aerobic Copper Catalysis

Ohhyeon Kwon; Kenneth Virgel N. Esguerra; Michael Glazerman; Laurène Petitjean; Yalun Xu; Xavier Ottenwaelder; Jean-Philip Lumb

doi:10.1055/s-0036-1588761

Synlett, Inhaltsverzeichnis

Synlett 2017; 28(13): 1548-1553
DOI: 10.1055/s-0036-1588761

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Development of 3,5-Di-tert-butylphenol as a Model Substrate for Biomimetic Aerobic Copper Catalysis

Ohhyeon Kwon

^aDepartment of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec, H3A 0B8, Canada eMail: jean-philip.lumb@mcgill.ca

,

Kenneth Virgel N. Esguerra

^aDepartment of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec, H3A 0B8, Canada eMail: jean-philip.lumb@mcgill.ca

,

Michael Glazerman †

^bDepartment of Chemistry and Biochemistry, Concordia University, 7141 Sherbrooke Street West, Montreal, Quebec, H3A 0B8, Canada eMail: dr.x@concordia.ca

,

Laurène Petitjean

^aDepartment of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec, H3A 0B8, Canada eMail: jean-philip.lumb@mcgill.ca

,

Yalun Xu

^aDepartment of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec, H3A 0B8, Canada eMail: jean-philip.lumb@mcgill.ca

,

Xavier Ottenwaelder

^bDepartment of Chemistry and Biochemistry, Concordia University, 7141 Sherbrooke Street West, Montreal, Quebec, H3A 0B8, Canada eMail: dr.x@concordia.ca

,

Jean-Philip Lumb *

^aDepartment of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec, H3A 0B8, Canada eMail: jean-philip.lumb@mcgill.ca

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Abstract

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^† In memoriam

Abstract

We develop 3,5-di-tertbutylphenol as a strategic substrate for the evaluation of biomimetic Cu₂–O₂ complexes intended to mimic the activity of tyrosinase. We describe a practical and scalable synthesis and validate its use in an aerobic ortho-oxygenation catalyzed by N,N′-di-tert-butylethylenediamine and [Cu(CH₃CN)₄]PF₆.

Key words

aerobic oxidation - biomimetic catalysis - copper - dearomatization - tyrosinase - oxidative coupling - oxepinobenzofuran

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Referenzen

References and Notes

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23 $157.50 CAD/mg at the time of writing, Sigma-Aldrich catalogue #PH000046.
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27 Synthesis of 3 via Borylation and Oxidation NOTE – caution should always be taken when performing large-scale oxidations. Risks are minimized here by carefully controlling the rate of addition of Oxone^®. A 250 mL round-bottom flask equipped with a Teflon-coated magnetic stir bar was charged with 8 (26.9 g, 100 mmol, 1 equiv), Mg turnings (3.65 g, 150 mmol, 1.5 equiv), and a piece of I₂ crystal. The reaction was put under N₂, and dry, degassed THF (100 mL) was added to the flask. The mixture was stirred at r.t. until initiation of the reaction was visible. An ice bath was used for cooling the reaction in the event that the temperature rose too high. In a separate 500 mL round-bottom flask equipped with a Teflon-coated magnetic stir bar, B(OMe)₃ (21.2 mL, 200 mmol, 2 equiv) was added via syringe, followed by the addition of THF (100 mL). The solution was cooled to 0 °C using an ice bath, and stirred under N₂. The THF solution of the Grignard reagent was transferred to the cooled flask containing the B(OMe)₃ solution via cannula. Once the addition was complete, the reaction was stirred vigorously and warmed back to r.t. for 2 h. The reaction was then cooled back down to 0 °C and quenched by the addition of 1 M HCl (80 mL). The solution was extracted using EtOAc (3 × 200 mL), the organic layers were combined, and dried over MgSO₄. The crude reaction mixture was concentrated in vacuo to give a yellow solid. This was transferred to a 2 L round-bottom flask equipped with a Teflon-coated magnetic stir bar, re-dissolved in acetone (600 mL), and an aq solution of Oxone^® (61.5 g, 200 mmol, 2 equiv in 600 mL H₂O) was added dropwise at r.t. over 1 h, and stirred for another 7 min. The reaction was then carefully quenched by the addition of sat. aq NaHSO₃ (200 mL), and concentrated in vacuo to remove most of the acetone. The crude reaction mixture was extracted with CH₂Cl₂ (3 × 200 mL), the organic layers were combined, dried over MgSO₄, and concentrated in vacuo to obtain a yellow solid. Flash column chromatography (hexanes–EtOAc, gradient from 100:0 to 90:10) yielded 3 as a yellow solid (18.7 g, 90% before recrystallization), and it was recrystallized from hexanes (50 mL) to yield pure 8 as colorless crystals (16.5 g, 80%). ¹H NMR (500 MHz, CDCl₃): δ = 7.00 (t, J = 1.7 Hz, 1 H), 6.68 (d, J = 1.7 Hz, 2 H), 4.52 (br s, 1 H), 1.30 (s, 18 H) ppm. ¹³C NMR (125 MHz, CDCl₃): δ = 154.8, 152.7, 115.2, 110.0, 34.9, 31.5 ppm. Analytical data matches that of the commercially available material.
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