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Title: Cobalt-catalysed alkylative aldol cyclisations using trialkylaluminium reagents : rhodium-catalysed carbometallation of ynamides in the preparation of multisubstituted enamides
Author: Rudkin, Mairi Ellen
ISNI:       0000 0004 2725 7535
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2010
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The cobalt-catalysed alkylative aldol cyclisations of α,β-unsaturated amides with an appendant ketone were studied using a range of trialkylaluminium reagents. Investigations revealed that Co(acac)2·2H2O acts as an effective precatalyst for this transformation and the reaction provides β-hydroxylactam products containing three contiguous stereocentres with high levels of diastereoselection. The substrate scope of the reaction was explored and attempts were made to develop an asymmetric variant of this process. Two plausible reaction mechanisms have been proposed; the first invokes a π-allylcobalt species as a key intermediate in the reaction mechanism and the second involves a radical-mediated pathway. A stereochemical rationale for the observed relative stereochemistry of the β-hydroxylactam products has been discussed. II. Rhodium-Catalysed Carbometallations of Ynamides in the Preparation of Multisubstituted Enamides A highly stereo- and regioselective rhodium-catalysed carbozincation of ynamides using organozinc reagents has been disclosed. A careful examination of ligand effects on the rhodium catalyst yielded a complementary set of hydrozincation conditions. The alkenylzinc intermediates produced during the course of these reactions have been harnessed in further transformations with electrophilic species and in cross-couplings, thus providing access to multisubstituted enamides in a stereo- and regioselective fashion. Additionally, a rhodium-catalysed tandem carbometallation−conjugate addition with ortho-boronate substituted cinnamic acid derivatives has been described. The enamide−indene products were obtained in good yields and regioselectivities. Preliminary work has been undertaken on an asymmetric variant of this transformation and the initial results have been reported.
Supervisor: Lam, Hon Wai. Sponsor: GSK
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: trialkylaluminium reagents ; cobalt-catalysed alkylative aldol cyclisations ; ynamides ; carbozincation