Synlett
DOI: 10.1055/s-0037-1611767
cluster
© Georg Thieme Verlag Stuttgart · New York

Sulfoxide-Directed Iterative Assembly into Oligoarenes

Tomoyuki Yanagi
,
Keisuke Nogi
,
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan   Email: yori@kuchem.kyoto-u.ac.jp
› Author Affiliations
This work was supported by JSPS KAKENHI Grant Numbers JP16H04109, JP18H04254, JP18H04409, and JP18K14212. T.Y. acknowledges a JSPS Predoctoral Fellowship. H.Y. thanks The Mitsubishi Foundation for financial support.
Further Information

Publication History

Received: 01 January 2019

Accepted after revision: 10 February 2019

Publication Date:
28 March 2019 (eFirst)

Published as part of the Cluster Iterative Synthesis

Abstract

A series of oligoarenes have been synthesized via sulfoxide-based iterative dehydrogenative transformations. By utilizing the sulfinyl moieties as on/off-switchable directing groups, overreactions and/or undesired oligomerizations were completely suppressed. Since the dehydrogenative couplings were not hampered by steric hinderance, sterically encumbered oligoarenes were synthesized.

Supporting Information

 
  • References and Notes


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  • 16 Methylation of hydroxy groups; Typical procedure (GP2) The methylation of 8 to the corresponding ether 8′ is representative. A Schlenk tube was charged with 8 (540 mg, 1.26 mmol), K2CO3 (340 mg, 2.50 mmol), and acetone (3.0 mL). Iodomethane (117 µL, 1.89 mmol) was added, and the resulting solution was stirred at 60 °C. Progress of the reaction was monitored by TLC. After completion of the reaction, aqueous HCl (2 mL) was added and the resulting mixture was extracted with CH2Cl2 (3 × 5 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure to afford sulfide 8′ (491 mg, ca. 1.1 mmol) with some impurities. The 8′ was oxidized to the corresponding sulfoxide without further purification in accordance with GP3.
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  • 21 Annulative construction of benzofurans; Typical procedure (GP4) A modification of the procedure that we reported was used.[3] The synthesis of 15a is representative. A Schlenk tube was charged with 13 (93.1 mg, 0.20 mmol), alkenyl sulfoxide 14a (80.3 mg, 0.24 mmol), and CH2Cl2 (2.0 mL). To the tube was added trifluoroacetic anhydride (34 μL, 0.24 mmol), and the resulting solution was stirred at 25 °C for 1 h, before saturated aqueous NaHCO3 (12 mL) was added. The resulting biphasic solution was extracted with CH2Cl2 (3 × 2 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (hexane/EtOAc, 20:1) to give 15a (62.0 mg, 0.11 mmol, 54%) as a colorless oil.
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