English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Thesis

Enol Catalysis – Enantioselective Transformations via Bifunctional Brønsted Acid Promoted Enolization

MPS-Authors
/persons/resource/persons180743

Shevchenko,  Grigory A.
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

External Ressource
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

Shevchenko, G. A. (2018). Enol Catalysis – Enantioselective Transformations via Bifunctional Brønsted Acid Promoted Enolization. PhD Thesis, Universität zu Köln, Köln.


Cite as: http://hdl.handle.net/21.11116/0000-0002-B63E-C
Abstract
Enantiopure carbonyl compounds bearing tetrasubstituted α-stereogenic centers are versatile building blocks for the synthesis of pharmaceuticals, fragrances, and natural products. The direct synthesis of such motifs via asymmetric α-functionalization of the corresponding ketones is a major challenge in both metal- and organocatalysis. In this work we report on development of enol catalysis, a novel strategy allowing the direct enantioselective α-functionalization of carbonyl compounds via Brønsted acid promoted enolization. Within this thesis, we established the generality of this strategy in a variety of enantioselective C–C, C–N and C–O bond forming reactions using simple α-branched and unbranched ketones as substrates. Along the same line of research we developed a highly enantioselective Robinson annulation of 1,3-diketones that afforded derivatives of the synthetically valuable Wieland–Miescher ketone. Furthermore, this strategy was successfully applied to direct α-amination and α-hydroxylation reactions using either diazocarboxylates or nitrosobenzene as reagents. And finally, we discovered that enol catalysis enables serendipitously-discovered α-aryloxylation of ketones using 1,4-benzoquinones. Taken together, this work has established enol catalysis as a generic enantioselective and scalable methodology applicable to a broad scope of challenges of organic synthesis.