English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Other

Strong and Confined Acid Catalysts Impart Stereocontrol onto the Non-Classical 2-Norbornyl Cation

MPS-Authors
/persons/resource/persons194757

Properzi,  Roberta
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons132871

Kaib,  Philip S. J.
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons132873

Leutzsch,  Markus
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons160168

Pupo,  Gabriele
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons188244

Mitra,  Raja
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons132969

De,  Chandra Kanta
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58764

List,  Benjamin
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

External Resource
No external resources are shared
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available
Citation

Properzi, R., Kaib, P. S. J., Leutzsch, M., Pupo, G., Mitra, R., De, C. K., et al. (2019). Strong and Confined Acid Catalysts Impart Stereocontrol onto the Non-Classical 2-Norbornyl Cation. doi:10.26434/chemrxiv.10887914.v1.


Cite as: http://hdl.handle.net/21.11116/0000-0005-9EB1-1
Abstract
Utilizing carbocationic intermediates in asymmetric transformations is a challenge for catalysis. While recent studies have provided promising approaches to systems proceeding through classical, trivalent carbenium ions, we were particularly intrigued by the possibility of imparting stereochemical control onto the 2-norbornyl cation, a small, fully aliphatic and positively-charged hydrocarbon that is known to adopt a non-classical structure. We now show that strong and confined imidodiphosphorimidate (IDPi) catalysts are competent acids for carrying out a n asymmetric stereoablative C–C bond forming reaction, utilizing racemic exo- or endo-norbornyl derivatives to exclusively obtain the highly enantioenriched exo-product. In addition, structurally-different substrates can be converted to the same product with remarkable enantioselectivities by leveraging the reactivity of a variety of functional groups. Mechanistic and kinetic studies suggest that all employed substrates proceed through a common cationic intermediate.