Synlett 2017; 28(19): 2609-2613
DOI: 10.1055/s-0036-1590937
cluster
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Fluorine-Containing Tetraarylanthracenes via Ruthenium-Catalyzed C–O or C–F Arylation and their Crystal Structures

Akiko Izumoto
a  Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan   Email: kakiuchi@chem.keio.ac.jp
,
Hikaru Kondo
a  Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan   Email: kakiuchi@chem.keio.ac.jp
,
Takuya Kochi
a  Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan   Email: kakiuchi@chem.keio.ac.jp
,
Fumitoshi Kakiuchi*
a  Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan   Email: kakiuchi@chem.keio.ac.jp
b  JST, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
› Author Affiliations
This work was supported in part by JSPS KAKENHI Grant Numbers JP15H05839 in Middle Molecular Strategy, and CREST and ACT-C (Grant Number JPMJCR12Y8) from the Japan Science and Technology Agency (JST), Japan. H.K. gratefully acknowledges the Japan Society for the Promotion of Science (JSPS) for a Research Fellowship for Young Scientists (JP16J02904). T.K. is also grateful for support by JSPS KAKENHI Grant Number 16H01040 (Precisely Designed Catalysts with Customized Scaffolding).
Further Information

Publication History

Received: 02 August 2017

Accepted after revision: 26 September 2017

Publication Date:
08 November 2017 (online)


Published as part of the Cluster C–O Activation

Abstract

Tetraarylanthracenes containing several fluoro groups were synthesized using the ruthenium-catalyzed C–O or C–F arylation with arylboronates and their structural and spectroscopic studies were conducted. The RuH2(CO)(PPh3)3-catalyzed C–O arylation of aromatic ketones was found to be effective for the introduction of aryl groups containing multiple fluoro groups. Anthracenes possessing fluorinated aryl groups were prepared in two steps from 1,4,5,8-tetramethoxyanthraquinone by C–O arylation and reduction of the carbonyl groups. A tetraphenylanthracene containing a fluorinated anthracene moiety was also prepared using C–F phenylation of octafluoroanthraquinone. Single-crystal X-ray diffraction analysis showed that the positions of fluoro groups on the tetraarylanthracenes lead to notable difference in the crystal packing structures. The larger difference between the tetraarylanthracenes was observed in the fluorescence spectra in the solid state than those in chloroform.

Supporting Information

 
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  • 10 Typical Procedure for C–O Tetraarylation of 8 (Table [3], Entry 2) To an oven-dried 20 mL Schlenk tube was added 1,4,5,8-tetramethoxyanthraquinone (8, 0.25 mmol), arylboronate 2c (2.5 mmol), RuH2(CO)(PPh3)3 (0.05 mmol), and 2 mL of dry p-xylene. The resulting mixture was heated at 150 °C for 20 h and cooled to room temperature. The crude material was passed through a basic aluminium oxide column to remove the remaining arylboronate. Tetraarylation product 5c (248 mg, 76%) was obtained as a yellow solid after purification by silica gel column chromatography (hexane/AcOEt = 15:1); mp 220–223 °C (dec.). 1H NMR (400 MHz, CDCl3): δ = 6.98–7.00 (m, 4 H), 7.05–7.10 (m, 4 H), 7.16–7.23 (m, 4 H), 7.53 (s, 4 H). 13C NMR (100 MHz, CDCl3): δ = 117.2 (d, J = 17.9 Hz), 117.7 (d, J = 17.9 Hz), 124.6 (dd, J = 6.6, 3.8 Hz), 134.6, 135.2, 136.4 (dd, J = 6.1, 4.2 Hz), 140.0, 149.9 (dd, J = 249.0, 11.8 Hz), 150.1 (dd, J = 250.0, 10.8 Hz), 186.2. IR (KBr): 3773 (w), 3062 (w), 2925 (w), 2345 (w), 1941 (w), 1658 (s), 1610 (m), 1522 (s), 1465 (m), 1422 (m), 1315 (m), 1268 (s), 1119 (m), 1028 (m), 893 (m), 816 (s), 767 (m) cm–1. HRMS (DART-TOF): m/z [M + H]+ calcd for C38H17F8O2: 657.1101; found: 657.1105.
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    • Selected recent publications on relationships between packing structures and solid-state fluorescence properties:
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