Highly stereo- and regioselective rhodium-catalysed carbometallations of ynamides using organometallic reagents have been disclosed. The scope of the process was explored, and investigations revealed that Rh(cod)(acac) acts as an effective precatalyst for carbometallation of ynamides using a range of organozinc reagents. A plausible mechanism has been suggested where an alkenylzinc intermediate is formed. This species has been exploited in further transformations with electrophiles and in cross-coupling reactions, thus providing access to multisubstituted enamides in a stereo- and regioselective manner. It was also possible to carry out the carbometallation of ynamides using organoboron reagents by using [Rh(cod)(MeCN)2]BF4 as a precatalyst. This complementary protocol allowed the introduction of a greater diversity of substituents, including those carrying sensitive functional groups. Mechanistic studies, including deuterium labelling, suggested that an alkenylrhodium intermediate was produced during the course of the reaction. With a set of optimised conditions, this species was successfully used in a tandem carbometallation– conjugate addition (or annulation) reaction with bifunctional arylboron reagents. The 2-amidoindene products were obtained in good yields and high regioselectivities. Preliminary studies on the development of an asymmetric variant of this transformation have been undertaken and the initial results have been reported. In addition, highly enantioselective dihydroxylation of the enamide substrates prepared from the developed rhodium-catalysed carbometallations of ynamides was readily accomplished using commercially available AD-mix- . This novel procedure provides an access to a wide range of chiral products that might be difficult to access using existing methods. Finally, as a further exemplification of asymmetric enamide dihydroxylation, this method was applied to a concise total synthesis of the antifugal natural product (+)-Tanikolide.

In this master thesis 1,2-disubstituted cyclopentadienes were prepared by method composed of three transition metal catalysed reactions. Then, the cyclopentadienes were converted into cyclopentadienyl manganese, rhenium and iron complexes. A one-pot synthesis of the cyclopentadienyl metal complexes was developed without isolation of the intermediate cyclopentadienes. The second goal of this thesis was preparation of vinyl-substituted cyclopentadienes using ring closing enyne metathesis. The last part of thesis dealt with synthesis of a chiral cyclopentadiene and preparation of the corresponding metal complexes. The important part of this work was preparation of starting materials using palladium catalysed cross-coupling reactions. Key words: cyclopentadienes, carbometallation, cross-coupling, metathesis, metallocenes.