TY - JOUR
T1 - Amino-Functionalization of Vinyl-Substituted Aromatic Diimides by Quantitative and Catalyst-Free Hydroamination**
AU - Sanematsu, Haruki
AU - Matsushita, Yoshitaka
AU - Takeuchi, Masayuki
AU - Takai, Atsuro
N1 - Funding Information:
We are grateful to Dr. Takashi Nakanishi (NIMS) for use of a workstation equipped with a Gaussian software, Ms. Shiho Iwata (NIMS) and Ms. Izumi Matsunaga (NIMS) for their help in the synthesis of precursor compounds, and Ms. Lara R. Holstein (NIMS) for giving comments on the manuscript. This research was supported by a Grant-in-Aid for Scientific Research (C) from JSPS 19K05640 to A.T., a Grant-in-Aid from Iketani Science and Technology Foundation 0311089-A to A.T., a Grant-in-Aid for Scientific Research on Innovative Areas “π-System Figuration” from JSPS (26102009 for M.T.), the MEXT “NIMS Molecule and Material Synthesis Platform” program, and Materials Analysis Station of NIMS.
Funding Information:
We are grateful to Dr. Takashi Nakanishi (NIMS) for use of a workstation equipped with a Gaussian software, Ms. Shiho Iwata (NIMS) and Ms. Izumi Matsunaga (NIMS) for their help in the synthesis of precursor compounds, and Ms. Lara R. Holstein (NIMS) for giving comments on the manuscript. This research was supported by a Grant‐in‐Aid for Scientific Research (C) from JSPS 19K05640 to A.T., a Grant‐in‐Aid from Iketani Science and Technology Foundation 0311089‐A to A.T., a Grant‐in‐Aid for Scientific Research on Innovative Areas “π‐System Figuration” from JSPS (26102009 for M.T.), the MEXT “NIMS Molecule and Material Synthesis Platform” program, and Materials Analysis Station of NIMS.
Publisher Copyright:
© 2020 Wiley-VCH GmbH
PY - 2021/1/13
Y1 - 2021/1/13
N2 - Development of facile and versatile synthetic tools for decorating π-conjugated molecules has attracted considerable interest because of their potential application in creating novel functional π-systems. Reported herein are quantitative catalyst-free hydroamination reactions of a series of aromatic diimide compounds having vinyl groups at the π-core, which have been confirmed by NMR, UV-vis absorption spectroscopy, mass analysis, and single-crystal X-ray structural analysis. Kinetic studies revealed that the hydroamination reaction of a vinyl-substituted naphthalenediimide with an aliphatic amine proceeded rapidly under benign conditions. Similarly, the two vinyl groups attached to aromatic diimides reacted with amines simultaneously, resulting in the formation of amine bisadducts and macromolecules. An amino group appended perylenediimide through an ethylene spacer at the π-core exhibited distinct fluorescence switching in response to acid and base.
AB - Development of facile and versatile synthetic tools for decorating π-conjugated molecules has attracted considerable interest because of their potential application in creating novel functional π-systems. Reported herein are quantitative catalyst-free hydroamination reactions of a series of aromatic diimide compounds having vinyl groups at the π-core, which have been confirmed by NMR, UV-vis absorption spectroscopy, mass analysis, and single-crystal X-ray structural analysis. Kinetic studies revealed that the hydroamination reaction of a vinyl-substituted naphthalenediimide with an aliphatic amine proceeded rapidly under benign conditions. Similarly, the two vinyl groups attached to aromatic diimides reacted with amines simultaneously, resulting in the formation of amine bisadducts and macromolecules. An amino group appended perylenediimide through an ethylene spacer at the π-core exhibited distinct fluorescence switching in response to acid and base.
KW - Michael addition
KW - aromatic diimide
KW - click chemistry
KW - electron-deficient π-system
KW - hydroamination
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U2 - 10.1002/chem.202003628
DO - 10.1002/chem.202003628
M3 - Article
C2 - 32896917
AN - SCOPUS:85097503511
VL - 27
SP - 934
EP - 938
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 3
ER -