Synlett 2017; 28(08): 957-961
DOI: 10.1055/s-0036-1588140
letter
© Georg Thieme Verlag Stuttgart · New York

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

Peter Franzmann
a  Johannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany   Email: [email protected]
,
Sebastian B. Beil
a  Johannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany   Email: [email protected]
b  Graduate School Materials Science in Mainz, Staudingerweg 9, 55128 Mainz, Germany
,
Peter M. Winterscheid
c  Bonn University, Kekulé Institute of Organic Chemistry and Biochemistry, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany
,
Dieter Schollmeyer
a  Johannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany   Email: [email protected]
,
Siegfried R. Waldvogel*
a  Johannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany   Email: [email protected]
b  Graduate School Materials Science in Mainz, Staudingerweg 9, 55128 Mainz, Germany
› Author Affiliations
Further Information

Publication History

Received: 06 December 2016

Accepted after revision: 09 January 2017

Publication Date:
02 February 2017 (online)


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.

Supporting Information

 
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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.