Search for: All records | NSF Public Access

Note: When clicking on a Digital Object Identifier (DOI) number, you will be taken to an external site maintained by the publisher. Some full text articles may not yet be available without a charge during the embargo (administrative interval).
What is a DOI Number?

Some links on this page may take you to non-federal websites. Their policies may differ from this site.

Catalytic Metal-free Allylic C–H Amination of Terpenoids

https://doi.org/10.1021/jacs.0c06997

Teh, Wei Pin ; Obenschain, Derek C. ; Black, Blaise M. ; Michael, Forrest E. ( September 2020 , Journal of the American Chemical Society)

Full Text Available
C−H Functionalization and Allylic Amination for Post‐Polymerization Modification of Polynorbornenes

https://doi.org/10.1002/anie.202303174

Gitter, Sean R. ; Teh, Wei Pin ; Yang, Xuejin ; Dohoda, Alexander F. ; Michael, Forrest E. ; Boydston, Andrew J. ( April 2023 , Angewandte Chemie International Edition)

Abstract
Post‐polymerization modification (PPM) via direct C−H functionalization is a powerful synthetic strategy to convert polymer feed‐stocks into value‐added products. We found that a metal‐free, Se‐catalyzed allylic C−H amination provided an efficient method for PPM of polynorbornenes (PNBs) produced via ring‐opening metathesis polymerization. Inherent to the mechanism of the allylic amination, PPM on PNBs preserved the alkene functional groups along the polymer backbone, while also avoiding transposition of the double bonds. Amination using a series of aryl sulfonamides led to good control over the degree of functionalization, access to a range of functionalities, and tunable thermal properties from the resulting polymers.

more » « less
C−H Functionalization and Allylic Amination for Post‐Polymerization Modification of Polynorbornenes

https://doi.org/10.1002/ange.202303174

Gitter, Sean R. ; Teh, Wei Pin ; Yang, Xuejin ; Dohoda, Alexander F. ; Michael, Forrest E. ; Boydston, Andrew J. ( April 2023 , Angewandte Chemie)

Abstract
Post‐polymerization modification (PPM) via direct C−H functionalization is a powerful synthetic strategy to convert polymer feed‐stocks into value‐added products. We found that a metal‐free, Se‐catalyzed allylic C−H amination provided an efficient method for PPM of polynorbornenes (PNBs) produced via ring‐opening metathesis polymerization. Inherent to the mechanism of the allylic amination, PPM on PNBs preserved the alkene functional groups along the polymer backbone, while also avoiding transposition of the double bonds. Amination using a series of aryl sulfonamides led to good control over the degree of functionalization, access to a range of functionalities, and tunable thermal properties from the resulting polymers.

more » « less