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Synthesis and stereochemistry of helical polyurethanes based on 2,2 '-dihydroxy-1,1 '-binaphthyl and diisocyanatobenzenes

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Title: Synthesis and stereochemistry of helical polyurethanes based on 2,2 '-dihydroxy-1,1 '-binaphthyl and diisocyanatobenzenes
Authors: Dai, Heshuang Browse this author
Shichibu, Yukatsu Browse this author
Imai, Yoshitane Browse this author
Hara, Nobuyuki Browse this author
Konishi, Katsuaki Browse this author
Wang, Yue Browse this author
Song, Zhiyi Browse this author →KAKEN DB
Nakano, Tamaki Browse this author →KAKEN DB
Issue Date: 14-Feb-2020
Publisher: Royal Society of Chemistry
Journal Title: Polymer chemistry
Volume: 11
Issue: 6
Start Page: 1134
End Page: 1144
Publisher DOI: 10.1039/c9py01348b
Abstract: Polyaddition between 2,2'-dihydroxy-1,1'-binaphthyl (BINOL) and 1,4-diisocyanatobenzene (14DIB) and that between BINOL and 1,3-diisocyanatobenzene (13DIB) were conducted leading to optically active, helical polyurethanes, poly(BINOL-alt-14DIB) and poly(BINOL-alt-13DIB), respectively. In BINOL-14DIB systems, cyclic dimers were formed along with helical, linear poly(BINOL-alt-14DIB) where the content of dimers was higher at a lower ee of BINOL and the yield of higher-molar-mass, linear polymers was higher at a higher ee of BINOL in feed. (R,R)-, (R,S)-, and (S, S)-Cyclic dimers were completely resolved and separated by chiral HPLC. The (R,S)-cyclic dimer was preferred over (R,R)-and (S, S)-cyclic dimers, while in the reaction using racemic BINOL, the (R,R)-cyclic dimer was preferred over the other isomers at 25-75% ee of (R)-BINOL in feed. Poly(BINOL-alt-14DIB) is proposed to be composed of sequences with rather contiguous (R)-BINOL units as the majority component with rather sporadically incorporated (S)-units as the minor component. Helical sense excess appears to be greater than expected from the ee of BINOL units in the chain, suggesting that (S)-BINOL units sporadically incorporated in a rather contiguous (R)-BINOL unit sequence become a part of the left-handed helical conformation controlled by the chiral influence of contiguous (R)-BINOL units. In addition, the chiral conformation of poly (BINOL-alt-14DIB) and BINOL-14DIB cyclic dimers appeared to be stabilized or enhanced in the solid state. The BINOL-13DIB systems produced linear dimers as major components of the dimer whose content was almost constant regardless of the ee of BINOL in feed. Poly(BINOL-alt-13DIB) is proposed to be composed of sequences with rather randomly distributed (R)- and (S)-BINOL units and may be characterized by sharp, left-handed turns based on BINOL chirality forming a longer-pitched, left-handed helix.
Type: article (author version)
Appears in Collections:触媒科学研究所 (Institute for Catalysis) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 中野 環

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