Asymmetric anionic polymerization of tris(trimethylsilyl)silyl methacrylate: a highly isotactic helical chiral polymer

Ishitake, Kenji; Satoh, Kotaro; Kamigaito, Masami; Okamoto, Yoshio

doi:10.1038/pj.2012.178

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Published: 17 October 2012

Polymer Synthesis and Reactions

Asymmetric anionic polymerization of tris(trimethylsilyl)silyl methacrylate: a highly isotactic helical chiral polymer

Kenji Ishitake¹,
Kotaro Satoh¹,
Masami Kamigaito¹ &
…
Yoshio Okamoto^2,3

Polymer Journal volume 45, pages 676–680 (2013)Cite this article

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Triarylmethyl methacrylate and related bulky methacrylates, such as triphenylmethyl (TrMA) methacrylate and 1-phenyldibezosuberyl methacrylate (PDBSMA), are known to yield highly isotactic and optically active polymers having a stable one-handed helical conformation via asymmetric anionic polymerization with a chiral initiating system.^{1, 2, 3, 4, 5, 6, 7, 8} The bulky triarylmethyl substituent dictates the helical conformation by forcing the chain end to propagate in an isospecific manner, and the chiral ligand or initiator determines the helix sense. These polymers show a high chiral recognition ability for racemic compounds and are utilized as chiral stationary phases for high-performance liquid chromatography.^{9, 10, 11, 12} However, all of these bulky substituents that are effective in helix-sense-selective and highly isotactic polymerizations are based on the triarylmethyl substituent or related skeletons;^{13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24} no other effective groups have been identified previously.

The tris(trimethylsilyl)silyl (TTMSS) group, also called the hypersilyl, sisyl, or supersilyl group,²⁵ is an extremely bulky silyl group and has recently been used to induce diastereoselectivity in various reactions, such as (2+2) cyclizations, Mukaiyama aldol reactions and cascade reactions of its enol ether by Yamamoto et al.^{26, 27, 28, 29} These bulky silyl ethers are stable under ionic conditions and can undergo various stereoselective organic reactions due to their highly bulky nature. Recently, we succeeded in synthesizing the novel highly bulky silyl methacrylate tris(trimethylsilyl)silyl methacrylate (TTMSSMA) from the sodium salt of methacrylic acid and supersilyl chloride. We also achieved highly isotactic radical polymerization (mm>90%) with this new methacrylate, for which the isotacticity is higher than that for TrMA and is slightly lower than that for PDBSMA.³⁰ We also achieved the facile transformation of the resulting polymers into isotactic poly(methacrylic acid) (PMAA) by removal of the silyl group.³¹ These results suggest that the TTMSS group in the methacrylate is sufficiently bulky to dictate the isotactic radical propagation, as is done by the triaryl group. The anionic polymerization of this novel bulky silyl methacrylate has not been studied previously. In contrast to the bulky silyl monomer, trimethylsilyl methacrylate, a protected methacrylic acid with a small silyl group, can be polymerized under anionic conditions^{32, 33, 34, 35, 36} to give stereoregular polymers that depend on the anionic initiating system.^{37, 38}

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Acknowledgements

This work was supported in part by JSPS Research Fellowships for Young Scientists for KI (No. 22-8509), a Grant-in-Aid for Young Scientists (S) for MK (No. 19675003) by the Japan Society for the Promotion of Science, and the Global COE Program ‘Elucidation and Design of Materials and Molecular Functions.’ We thank Mr Muennori Shimoyama, Dr Hiroki Iida and Professor Eiji Yashima (Nagoya University) for their technical support and useful suggestions on DRCD measurement.

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Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan
Kenji Ishitake, Kotaro Satoh & Masami Kamigaito
Nagoya University, Nagoya, Japan
Yoshio Okamoto
College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin, China
Yoshio Okamoto

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Kenji Ishitake
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Masami Kamigaito
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Correspondence to Masami Kamigaito.

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Ishitake, K., Satoh, K., Kamigaito, M. et al. Asymmetric anionic polymerization of tris(trimethylsilyl)silyl methacrylate: a highly isotactic helical chiral polymer. Polym J 45, 676–680 (2013). https://doi.org/10.1038/pj.2012.178

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Received: 07 May 2012
Revised: 19 July 2012
Accepted: 07 September 2012
Published: 17 October 2012
Issue date: June 2013
DOI: https://doi.org/10.1038/pj.2012.178

Asymmetric anionic polymerization of tris(trimethylsilyl)silyl methacrylate: a highly isotactic helical chiral polymer

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