Bay-Region-Selective Annulative π-Extension (APEX) of Perylene Diimides with Arynes

Takayuki Nakamuro; Kazushi Kumazawa; Hideto Ito; Kenichiro Itami

doi:10.1055/s-0037-1611668

Synlett, Table of Contents

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

Takayuki Nakamuro

^aGraduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan Email: ito.hideto@g.mbox.nagoya-u.ac.jp

,

Kazushi Kumazawa

^aGraduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan Email: ito.hideto@g.mbox.nagoya-u.ac.jp

,

Hideto Ito *

^aGraduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan Email: ito.hideto@g.mbox.nagoya-u.ac.jp

^bJST-ERATO, Itami Molecular Nanocarbon Project, Nagoya University, Chikusa, Nagoya 464-8602, Japan

,

Kenichiro Itami *

^aGraduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan Email: ito.hideto@g.mbox.nagoya-u.ac.jp

^bJST-ERATO, Itami Molecular Nanocarbon Project, Nagoya University, Chikusa, Nagoya 464-8602, Japan

^cInstitute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya 464-8602, Japan Email: itami@chem.nagoya-u.ac.jp

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Abstract

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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.

Key words

annulative π-extension - perylene diimides - arynes - Diels–Alder reaction - coronene diimides - polycyclic aromatic hydrocarbons

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References

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.

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