Thieme Chemistry Journals Awardees – Where Are They Now?Molybdenum(V)-Mediated Synthesis of Nonsymmetric Diaryl and Aryl Alkyl Chalcogenides

Peter Franzmann; Sebastian B. Beil; Peter M. Winterscheid; Dieter Schollmeyer; Siegfried R. Waldvogel

doi:10.1055/s-0036-1588140

Synlett, Table of Contents

Synlett 2017; 28(08): 957-961
DOI: 10.1055/s-0036-1588140

letter

Thieme Chemistry Journals Awardees – Where Are They Now?
Molybdenum(V)-Mediated Synthesis of Nonsymmetric Diaryl and Aryl Alkyl Chalcogenides

Peter Franzmann

^aJohannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany Email: waldvogel@uni-mainz.de

,

Sebastian B. Beil

^aJohannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany Email: waldvogel@uni-mainz.de

^bGraduate School Materials Science in Mainz, Staudingerweg 9, 55128 Mainz, Germany

,

Peter M. Winterscheid

^cBonn University, Kekulé Institute of Organic Chemistry and Biochemistry, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany

,

Dieter Schollmeyer

^aJohannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany Email: waldvogel@uni-mainz.de

,

Siegfried R. Waldvogel*

^aJohannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany Email: waldvogel@uni-mainz.de

^bGraduate School Materials Science in Mainz, Staudingerweg 9, 55128 Mainz, Germany

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Abstract

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Abstract

Oxidative chalcogenation reaction using molybdenum(V) reagents provides fast access to a wide range of nonsymmetric aryl sulfides and selenides. The established protocol is tolerated by a variety of labile functions, protecting groups, and aromatic heterocycles. In particular, when labile moieties are present, the use of molybdenum(V) reagents provides superior yields compared to other oxidants.

Key words

molybdenum pentachloride - oxidative coupling - C–S bond formation - cross-coupling - disulfides

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References

References and Notes

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28 General Protocol of the Disulfide Synthesis (A) A solution of the given thiol (1.0 equiv) in pyridine was treated with iodine (0.66 equiv) and stirred for the given time (15–30 min) at r.t. at argon atmosphere. Subsequently, water was added, and the mixture was extracted with EtOAc. The combined organic layers were washed with brine, dried over MgSO₄, and the solvent was evaporated. The crude product was purified as described below.
29 General Protocol of the Oxidative Coupling Reaction Using Mo(V) Reagents (B) A solution of the disulfide 5 (1.0 equiv) in anhydrous CH₂Cl₂ was treated with TiCl₄ (3.3 equiv) and subsequently MoCl₅ (3.0 equiv) or with MoCl₃(HFIP)₂ (3.0 equiv). Subsequently, a solution of the aromatic compound (5.0 equiv) in anhydrous CH₂Cl₂ was added dropwise,e and the mixture was stirred for the given time (10–60 min) at r.t. at argon atmosphere. After completion of the reaction, a sat. aq solution of NaHCO₃ was added and it was stirred for additional 5 min. The mixture was extracted with CH₂Cl₂, washed with brine, dried over MgSO₄, and the solvent was evaporated. The crude product was purified as described below.
30 Bis(4-iodophenyl)disulfide (5e) According to the protocol for the disulfide synthesis (A), 4-iodothiophenol (0.50 g, 2.12 mmol) was treated with iodine (0.36 g, 1.40 mmol) in pyridine (20 mL) for 15 min. The crude product was filtered through a pad of silica (eluent: cyclohexane–EtOAc, 9:1) to yield compound 5e as a colorless solid (0.44 g, 88%). ¹H NMR (400 MHz, CD₂Cl₂): δ = 7.65–7.62 (m, 4 H), 7.25–7.21 (m, 4 H). ¹³C NMR (101 MHz, CD₂Cl₂): δ = 138.7, 137.2, 129.9, 93.0. HRMS (APCI+): m/z calcd for C₁₂H₈I₂S₂ [M]^•+: 469.8151; found: 469.8160.
31 4-Methylphenyl-5′-bromo-2′-iodo-4′-methoxyphenylsulfide (8f) According to the protocol for the oxidative coupling reaction (B), bis(4-methylphenyl)disulfide (5b, 0.20 g, 0.81 mmol) was treated with TiCl₄ (0.51 g, 2.68 mmol) and MoCl₅ (0.66 g, 2.44 mmol) in anhydrous CH₂Cl₂ (20 mL). Subsequently, 2-bromo-5-iodoanisole (7f, 1.27 g, 4.06 mmol) in anhydrous CH₂Cl₂ (10 mL) was added dropwise, and the reaction mixture was stirred for 15 min. After the described workup, the crude product was purified by flash column chromatography (eluent: cyclohexane–EtOAc, 99:1) and recrystallized from MeOH (approx. 15 mL, 65 → 4 °C) to yield compound 8f as a colorless solid (0.37 g, 52%); mp 135.2–136.7 °C. ¹H NMR (400 MHz, CD₂Cl₂): δ = 7.38 (s, 1 H), 7.32 (s, 1 H), 7.32–7.20 (m, 2 H), 7.18–7.16 (m, 2 H), 3.87 (s, 3 H), 2.34 (s, 3 H). ¹³C NMR (101 MHz, CD₂Cl₂): δ = 155.8, 138.7, 135.5, 134.5, 131.9, 131.9, 130.9, 123.5, 113.1, 101.4, 57.3, 21.4. HRMS (ESI+): m/z calcd for C₁₄H₁₂OS⁷⁹BrI [M + H]⁺: 434.8915; found: 434.8924.

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