Advancing selectivity control with highly reactive organometallic reagents

Massimo Giannerini

Research output: ThesisThesis fully internal (DIV)

1770 Downloads (Pure)

Abstract

The high reactivity of hard organometallic reagents represents, at the same time, their main advantage and limitation. Therefor it is a main challenge for chemists to develop procedures capable of exploiting their strong reactivity while preventing side reactions to take place. In this work the control on the selectivity of Grignard and organolithium compounds, two of the most reactive organometallic compounds, is significantly extended in the field of Cu and Pd catalysed reactions. The selective generation of chiral Z olefins, unprecedented in Cu catalysed allylic alkylations with Grignard reagents, and the ligand induced regioselectivity inversion in Cu catalysed allylic alkylation with organolithium compounds are introduced in the first part of this work. The use of organolithium in Pd catalysed cross coupling with organo(pseudo)halides is reported in the second part. This reaction takes full advantage of the reactivity of organolithium compounds affording fast transformations that proceed under ambient conditions without the occurrence of side reactions. Considering the high synthetic versatility and ease in preparation of organolithium compounds, this methodology is a valuable tool to improve efficiency and time consume in Pd catalysed cross-coupling, one of the most frequently used C-C bond forming reactions.
Original languageEnglish
QualificationDoctor of Philosophy
Awarding Institution
  • University of Groningen
Supervisors/Advisors
  • Feringa, Ben L., Supervisor
Award date17-Apr-2015
Place of Publication[Groningen]
Publisher
Print ISBNs978-90-367-7793-3
Electronic ISBNs978-90-367-7792-6
Publication statusPublished - 2015

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