Chapter 1. Effect of linker length on selectivity and cooperative reactivity in platinum-catalyzed asymmetric alkylation of bis(phenylphosphino)alkanes. The selectivity of catalytic asymmetric transformations of bifunctional symmetrical substrates often depends on the linker between the two reactive sites. If the catalyst controls the selectivity of reactions at both sites, the rac product will be formed in high enantiomeric ratio (er) via asymmetric amplification. Substrate control may augment this selectivity (positive cooperativity) or detract from it (negative cooperativity). We investigated the effect of linker length on the selectivity of catalytic asymmetric alkylation of the bis(secondary phosphines) PhHP-(CH2)[subscript n]PHPh (n = 2-6, 1a-e) with benzyl bromide using the base NaOSiMe3 and the catalyst precursor Pt((R,R)-Me-DuPhos)(Ph)(Cl). The two alkylations of bis(secondary phosphines) 1b-e with longer linker lengths (n = 3-6) showed identical selectivity, within experimental error. This catalyst control resulted in asymmetric amplification of rac-2. In contrast, the selectivity of the first alkylation of ethano-bridged 1a was lower than that in 1b-e (negative cooperativity), but the selectivity of the second alkylation increased due to positive cooperativity. I developed an efficient synthesis of the intermediate PhHP(CH2)2PPh(CH2Ph) (3a), which was required for determination of the selectivity of both steps in Pt-catalyzed alkylation of 1a. Possible mechanistic explanations for the observed dependence of selectivity on linker length are discussed in this chapter. Chapter 2. Selective formation of a C3-symmetric P-stereogenic tris(phosphine) via platinum-catalyzed asymmetric alkylation of a tris(secondary phosphine). C2-symmetric bis(phosphines) are the most common and successful ligands for metal-catalyzed reactions. Considering the great success of C2-symmetric ligands in asymmetric catalysis, C3-symmetric chiral tris(phosphines) were proposed to be useful in octahedral complexes, creating three homotopic sites. However, very little is known about C3-symmetric tris(phosphines) and their applications, mostly because of the lack of synthetic routes. We used Pt-catalyzed asymmetric alkylation to prepare enantiomerically enriched C3-symmetric, P-stereogenic tripodal tris(phosphines) from the tris(secondary phosphine) MeC(CH2PHPh)3 (5 a racemic mixture of C1- and C3-symmetric diastereomers) and a benzl bromide, utilizing the Pt((R,R)-Me-Duphos)(Ph)(Cl) catalyst precursor and a base. Pt-catalyzed alkylation of MeC(CH2PHPh)3 (5) with 2-cyanobenzyl bromide gave a mixture of tris(phosphines) MeC(CH2PPh(CH2Ar))3 (6) enriched in C3-6; oxidation of 6 by sulfur or H2O2 formed phosphine sulfide S-6 and oxide O-6. Hydrogen bonding between O-6 and the chiral amino acid (S)-Fmoc-Trip(BOC)-OH leads to the formation of new diastereomers. By integrating the 31P NMR spectra, I measured the dr and er values. Tris(phosphine) 6 was formed with a disatereomeric ratio (dr - C3/C1) of 2.1(2) and enantiomeric ratios of 54(10) and 3.8(7) for C3-3 and C1-3 respectively, which showed that the selectivity of the triple alkylation was not the same at each site (substrate control). Chapter 3. Screening racemic catalysts provides information on selectivity and mechanism in platinum-mediated asymmetric alkylation of bis- and tris(secondary phosphines). Screening racemic catalysts for transformations of symmetrical bifunctional substrates can provide information on the selectivity of an enantiopure catalyst. This idea was extended to Pt-catalyzed asymmetric alkylation of the bis(secondary phosphines) PhHP(CH2)3PHPh and PhHPCH2CMe2CH2PHPh and the tris(phosphine) MeC(CH2PHPh)3 with benzyl bromides using the catalyst precursors Pt(Me-DuPhos)(Ph)(CI) and Pt(BenzP*)(Ph)(CI). Depending on the catalyst and the substrate, these reactions occured under catalyst control without dissociation of the substrate, or under substrate control with or without substrate dissociation. The resulting structure-selectivity relationships provided mechanistic information. Chapter 4. Synthesis of new chiral bis(phospholane) metal-pincer complexes. Metal pincer complexes have received great attention in recent years as robust catalyst precursors. However, chiral metal pincer complexes for application in asymmetric catalysis are rare. Dialkylphospholane groups have an outstanding track record in asymmetric catalysis (commercial DuPhos and BPE ligands) and their steric properties can be easily controlled by tuning the alkyl substituents on the phospholane ring. These donors have similar steric and electronic properties to the common used bulky dialkylphosphine groups (P(t-Bu)2, P(i-Pr)2, etc.). Optimization of the synthesis of chiral PCP ligands bearing such phospholane groups and investigation of their coordination chemistry are discussed in this chapter.