Izvleček: | <p>In this thesis, we describe a range of rhodium-catalysed regio- and enantioselective Suzuki-Miyaura type cross-coupling reactions. Brief elaborations of products and modifications of drug molecules and natural products are demonstrated to show the utilities of these methodologies.</p>
<p>In Chapter 1, transition-metal-catalysed asymmetric Suzuki-Miyaura cross-coupling reactions are introduced in sequence, categorised by transition-metal type. Recent highlights in this area are discussed and the future of asymmetric Suzuki-Miyaura cross-coupling reactions is outlined.</p>
<p>In Chapter 2, we present the rhodium-catalysed regio- and enantioselective Suzuki-Miyaura cross-coupling reactions between vinylethylene carbonate and (hetero)arylboronic acids. We proposed that the chelation of substrate would help the regiocontrol. Combined experimental and computational mechanistic studies reveal the formation of a six-membered rhoda-1,3-dioxa-2-one intermediate after S<sub>N</sub>2’ oxidative addition during catalytic cycle, which is crucial for the regio- and enantiocontrol.</p>
<p>In Chapter 3, the method shown in Chapter 2 is elaborated by changing the ligand and solvent. The reaction scope now includes methyl-substituted vinylethylene carbonate. Notably, this represents the first examples of acyclic quaternary stereogenic centres formations via Rh-catalysed cross-coupling reactions between racemic tertiary electrophiles and achiral nucleophiles. The synthetic utilities of this method are demonstrated with formal syntheses of drug candidate and natural products (+)-epilaurene and (−)-cuparene.</p>
<p>In Chapter 4, we describe a series of general and modular regio- and enantioselective allylic arylation reactions. Unlike Chapter 2 and Chapter 3, the regioselectivities in this chapter are completely controlled by the rhodium/ligand complex. This method consistently produced arylation products in high levels of yield and selectivities (typically >90% yield, >95% ee and >20:1 r.r.). The synthetic applicability of these transformations is demonstrated with late-stage-functionalisations of naproxen, (−)-citronellal, (−)-perillaldehyde and estrone.</p>
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