CC BY-ND-NC 4.0 · Synlett 2019; 30(04): 423-428
DOI: 10.1055/s-0037-1611668
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Bay-Region-Selective Annulative π-Extension (APEX) of Perylene Diimides with Arynes

a  Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan   Email: ito.hideto@g.mbox.nagoya-u.ac.jp
,
Kazushi Kumazawa
a  Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan   Email: ito.hideto@g.mbox.nagoya-u.ac.jp
,
a  Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan   Email: ito.hideto@g.mbox.nagoya-u.ac.jp
b  JST-ERATO, Itami Molecular Nanocarbon Project, Nagoya University, Chikusa, Nagoya 464-8602, Japan
,
a  Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan   Email: ito.hideto@g.mbox.nagoya-u.ac.jp
b  JST-ERATO, Itami Molecular Nanocarbon Project, Nagoya University, Chikusa, Nagoya 464-8602, Japan
c  Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya 464-8602, Japan   Email: itami@chem.nagoya-u.ac.jp
› Author Affiliations
This work was supported by the ERATO program from JST (JPMJER1302 to K.I.), JSPS KAKENHI Grants 18J01322 to T.N. and JP26810057, JP16H00907, JP17K19155, and JP18H02019 to H.I., the SUMITOMO Foundation (141495 to H.I.), and the DAIKO Foundation (H.I.).
Further Information

Publication History

Received: 30 November 2018

Accepted after revision: 10 January 2019

Publication Date:
07 February 2019 (eFirst)

  

Published as part of the 30 Years SYNLETT – Pearl Anniversary Issue

Abstract

A bay-region-selective annulative π-extension (APEX) reaction of perylene diimides (PDIs) has been achieved by means of in-situ generated reactive aryne intermediates. This method provides an efficient one-pot π-extension at the short axis of PDIs in a sequential manner. Mechanistically, an inverse-electron-demand Diels–Alder reaction might be operative for the transformation.

Supporting Information

 
  • References and Notes

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  • 17 3a; Typical Procedure A screw-capped glass tube containing a magnetic stirrer bar was charged sequentially with the dimesityl PDI 1a (100 μmol, 1.0 equiv, 62.4 mg), KF (0.51 mmol, 5.0 equiv, 29.5 mg), PhCN (2.0 mL), and 2-(trimethylsilyl)phenyl triflate (2a, 0.20 mmol, 2.0 equiv, 60.0 mg) under a stream of N2. The mixture was stirred at 160 °C for 48 h, cooled to r.t., and passed through a short pad of silica gel (eluent: CHCl3). The organic solvent was removed under reduced pressure to give a crude mixture that was analyzed by 1H NMR (CDCl3) with CH2Br2 as an internal standard. The residue was the purified by flash column chromatography (silica gel) to afford a mixture of 3aa and 4aa, which was further purified by gel-permeation chromatography to give 3aa as a red solid; yield: 26.4 mg (37.7 μmol, 37% isolated). 1H NMR (400 MHz, CDCl3): δ = 10.2 (s, 2 H), 9.32–9.27 (m, 2 H), 9.24 (d, J = 8.4 Hz, 2 H), 9.10 (d, J = 8.4 Hz, 2 H), 8.19–8.13 (m, 2 H), 7.13 (s, 4 H), 2.42 (s, 6 H), 2.25 (s, 12 H). 13C NMR (150 MHz, CDCl3): δ = 163.5, 163.3, 138.8, 135.2, 134.2, 131.1, 130.0, 129.51, 129.47, 129.3, 129.2, 129.0, 128.6, 127.9, 125.1, 124.2, 123.3, 122.9, 122.5, 21.3, 17.9. HRMS (MALDI-TOF): m/z [M + H]+ calcd for C48H33N2O4: 701.2435; found: 701.2434.