Synlett
DOI: 10.1055/a-1352-1605
synpacts

Stereoretentive Olefin Metathesis: A New Avenue for the Synthesis of All-cis Poly(p-phenylene vinylene)s and Stereo­defined Polyalkenamers

Samuel J. Kempel
,
Ting-Wei Hsu
,
This work was funded by the Petroleum Research Fund managed by the American Chemical Society under Grant Number 60540-DN17 and by the Welch Foundation under Grant Number (A-2004-20190330).


Abstract

Olefin metathesis has tremendously impacted all fields of synthetic chemistry. However, the control of the olefin stereochemistry during this process remains a grand challenge. Recent innovations in catalyst design have permitted control of the stereochemistry of the olefin product. Here, we discuss the development of stereoretentive olefin metathesis, with an emphasis on the synthesis of stereodefined polyalkenamers through ring-opening metathesis polymerization (ROMP). We then present our application of this unique reaction manifold to the preparation of all-cis poly(p-phenylene vinylene)s (PPVs). A dithiolate Ru catalyst was found to deliver perfect cis selectivity for the polymerization of a paracyclophane diene monomer. By using optimized conditions, all-cis PPVs with narrow dispersities and predictable molar masses were obtained by varying the ratio of monomer to catalyst. The high chain fidelity of the stereoretentive ROMP with a paracyclophane diene monomer enabled the preparation of well-defined diblock copolymers with a norbornene co-monomer. Photochemical isomerization of all-cis to all-trans PPVs was effected with both homopolymers and diblock copolymers. This process was shown to be selective for the PPV block, and resulted in changes in optical properties, polymer size, and solubility. Stereoretentive ROMP provides a promising platform for synthesizing polymers with unique properties, including photoresponsive all-cis PPVs with living characteristics.

1 Introduction

2 Synthetic Applications of Stereoretentive Olefin Metathesis

3 Stereocontrol of Polyalkenamers through Stereoretentive ROMP

4 Stereoretentive ROMP To Access All-cis Poly(p-phenylene vinylene)s

5 Conclusion



Publication History

Received: 22 December 2020

Accepted after revision: 12 January 2021

Publication Date:
12 January 2021 (online)

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
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