Exploitation of Unconventional Electrophiles in Enantioselective Pd(0)-Catalyzed C-H Functionalizations

Asymmetric metal-catalyzed C-H functionalization has enjoyed great success as a powerful strategy for the rapid construction of elaborate structures from simple precursors. For example, aryl (pseudo)halides have been extensively employed as electrophilic substrates in enantioselective Pd(0)-catalyzed syntheses of heterocycles. However, alternative substrates for C-H functionalizations are far less developed. This thesis focuses on the exploration of unconventional electrophilic partners for asymmetric Pd(0)-catalyzed C-H functionalizations, allowing access to relevant N-heterocyclic scaffolds. An enantioselective functionalization of readily accessible ketene aminal phosphates resulted in the formation of versatile isoindolines. A new class of bulky electron-rich phosphine ligands, designed explicitly for this transformation, enabled efficient functionalization at ambient temperature, resulting in high enantioselectivities of the desired products. Employing perfluoroalkyl imidoyl chlorides as electrophilic partners gave rise to previously inaccessible chiral 1H-isoindoles. The C-H functionalization strategy not only enabled efficient asymmetric construction of three-dimensional structures with functional exit vectors but also allowed the products to be additionally decorated with a perfluoroalkyl group and a quaternary stereogenic center.


Advisor(s):
Cramer, Nicolai
Year:
2019
Publisher:
Lausanne, EPFL
Keywords:
Laboratories:
LCSA


Note: The status of this file is: EPFL only


 Record created 2019-03-27, last modified 2019-06-17

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