Configurationally Chiral SuFEx-Based Polymers

Dong-Dong Liang; Sidharam P Pujari; Muthusamy Subramaniam; Maarten Besten; Han Zuilhof

doi:10.1002/anie.202116158

Configurationally Chiral SuFEx-Based Polymers

Angew Chem Int Ed Engl. 2022 Feb 14;61(8):e202116158. doi: 10.1002/anie.202116158. Epub 2022 Jan 11.

Authors

Dong-Dong Liang¹, Sidharam P Pujari¹, Muthusamy Subramaniam^{1

2}, Maarten Besten¹, Han Zuilhof^{1

2

3}

Affiliations

¹ Laboratory of Organic Chemistry, Wageningen University, Stippeneng 4, 6708WE, Wageningen, The Netherlands.
² School of Pharmaceutical Science and Technology, Tianjin University, 92 Weijin Road, Tianjin, 300072, China.
³ Department of Chemical and Materials Engineering, Faculty of Engineering, King Abdulaziz University, Jeddah, 21589, Saudi Arabia.

Abstract

Novel methods to make synthetic chiral polymers are highly desirable given their potential in a rapidly increasing number of bio-inspired applications. The enantiospecific sulfur-fluorine exchange (SuFEx) reaction of chiral di-sulfonimidoyl fluorides (di-SFs) with diphenols, was used to produce high-molecular-weight chiral polymers with configurational backbone chirality. The resulting new class of polymers, polysulfonimidates, can be efficiently produced via this step-growth mechanism for a wide range of di-SFs and diphenols, yielding M_n^PS up to 283 kDa with a typical dispersity Đ around 1.6. The optical activity of the resulting chiral polymers is largely due to the intrinsic asymmetry of the S atoms (configurational chirality). Finally, the enantiospecificity (ee>98 %) of the polymerization reaction was demonstrated by the degradation of a disulfide-containing polysulfonimidate. This novel route towards configurational main-chain chirality opens up new approaches towards tailor-made chiral polymers with precisely defined properties.

Keywords: Chiral Polymer; Click Chemistry; Enantiospecific; Polysulfonimidates; SuFEx Reaction.

Publication types

Research Support, Non-U.S. Gov't