Main group species for catalytic hydroboration
Date
29/11/2018Author
Bismuto, Alessandro
Metadata
Abstract
Modern synthetic chemistry is unimaginable without transition metal catalysis. Yet the
often high cost, toxicity and scarcity of many transition metals is driving attempts to find
sustainable alternatives. Thus, the development of catalytic processes using main-group
catalysts is now of broad interest. This thesis reports the development of a facile protocol
for the aluminium-catalysed hydroboration of alkynes, alkenes and polar bonds using
commercially-available catalysts. The catalytic hydroboration is proposed to occur by
hydroalumination followed by product release through σ-bond metathesis with pinacol
borane. An alternative route to alkenyl boranes is the 1,1-carboboration of alkynes using
stoichiometric B(C6F5)3. A zwitterionic intermediate in the Piers’ borane-catalysed
hydroboration and 1,1-carboboration of alkynes with B(C6F5)3 has been characterised
and its divergent reactivity identified. This has led to the development of a B(C6F5)3 -
catalysed hydroboration of alkynes using HBpin.