The thesis entitled “Studies on the Stereoselective Geminal and Vicinal Heterodifunctionalization of Alkenes” consists of three chapters. Chapter 1: Part A: Bromonium Ion Mediated Stereoselective Geminal Aminooxygenation of Vinylarenes In this part (part-A) of Chapter 1, the development and mechanistic studies of the first method for the non-Wacker intermolecular geminal aminooxygenation of vinylarenes (styrenes) has been presented (Scheme 1). Sheme 1 The role of the substituent on controlling the competitive vicinal and geminal addition pathways has been studied. It was found that the unsubstituted amino alcohol takes both the vicinal addition pathways, whereas, the introduction of substituent on the aminoalcohols was found to favour only the geminal addition route (Scheme 2). Scheme 2 The diastereomeric alkenes were found to show stereoconvergence on the product formation. The migration of the phenyl group in the semipinacol rearrangement was confirmed by deuterium labeling studies. This highly stereoselective oxidative geminal addition is found to involve a semipinacol rearrangement (Scheme 3). Scheme 3 Chapter 1: Part B: Bromonium Ion Mediated Stereoselective Anti-Markovnikov Geminal Diamination and Dioxygenation of Vinylarenes In this part (part-B) of Chapter 1, the development of a facile straightforward method for the stereoselective intermolecular geminal diamination of vinylarenes under the bromonium ion mediated conditions is discussed (Scheme 4). Scheme 4 The addition of unsubstituted diamine was found to follow both geminal and vicinal addition routes, while the introduction of the substituent on the diamine was found to favour only geminal addition (Scheme 5). Scheme 5 The stoichiometric geminal dioxygenation of vinylarenes using 1,2 and 1,3 -diols was also found to work well. The substituent on the nucleophile and the nucleophilicity of the heteroatom was found to control the competitive geminal and vicinal addition pathways. The stereoselectivity of geminal dioxygenation is dependent on the ring size of the product formed and on the position of the stereo-inducing substituent. Unlike the unsubstituted diamine and the unsubstituted aminoalcohol, irrespective of the substituents attached to it, the 1,2-diols furnished only the geminal addition product (Scheme 6). Scheme 6 Interestingly, the α-methyl substituted 1,3-diols provided the corresponding 2,4-disubstituted 1,3-dioxanes with very high stereoselectivity. The β-propyl substituted 1,3-diol gave the 2,5-disubstituted 1,3-dioxane as a mixture of diastereomers (Scheme 7). Scheme 7 The phenyl migration in the semi-pinacol rearrangement in the geminal addition process was confirmed from the deuterium labelling studies (Scheme 8). Scheme 8 Chapter 1: Part C: Straightforward Synthesis of 1,3-Dioxolan-4-ones through Geminal Difunctionalization of Vinylarenes The development of a straightforward method for the synthesis of important chiral synthon, 1,3-dioxolan-4-ones by the geminal addition of α-hydroxy carboxylic acids to vinylarenes has been presented in the final part of this chapter (part-C, Chapter 1) (Scheme 9). Scheme 9 The effect of substituents on the α-hydroxy carboxylic acid on controlling the stereoselectivity of the reaction has been studied. In the case of α-hydroxy carboxylic acid derived from isoleucine containing the chiral substituent at the α position, it exclusively forms a single diastereomer of the corresponding 1,3-dioxolan-4-one (Scheme 10). Scheme 10 The reactions of α-hydroxy carboxylic acids with styrenes containing a variety of substituents have been found to work well, including the styrenes containing the electron withdrawing groups and the β-substituted styrenes. The migration of the phenyl group in the semi-pinacol rearrangement in the geminal oxidative reaction has been confirmed by deuterium labelling studies (Scheme 11). Scheme 11 Simple carboxylic acids are found to form only the vicinal addition products on reaction with styrenes. However, the alcohols under the same conditions formed only the geminal addition product, thereby demonstrating the role of nucleophilicty of heteroatom being added that control the competitive vicinal and geminal addition pathways (Scheme 12 Scheme 12 Chapter 2: Reagent-Switch Controlled Metal-Free Geminal Difunctionalization of Vinylarenes In this Chapter, the development of two new methods for the geminal oxyamination of vinylarenes and the detailed studies to understand their mechanism are presented. A novel reagent-switch for the control of migrating group by controlling the two independent, distinct pathways of the two reagent systems has been reported for this geminal addition (Scheme 13). Scheme 13 We have developed the first general method for the geminal diamination of vinylarenes with excellent stereoselectivity mediated by a hypervalent iodine reagent (Scheme 14). Scheme 14 This method is also found to be very efficient for the stoichiometric metal-free geminal dioxygenation of vinylarenes (Scheme 15). Scheme 15 The substituent on the nucleophile and the nucleophilicity of the heteroatom was found to control the competitive geminal and vicinal addition pathways. Chapter 3: Studies on the Synthesis of Enantiopure Morpholine Derivatives Mediated by Dimethyl (Methylthio) Sulfonium Triflate (DMTST) In this chapter, the development of a sulfonium ion mediated cylco-etherification methodology for the construction of biologically important molecules such as morpholines, morpholine carboxylates and morpholine methylthio ethers in good yields under mild conditions using DMTST has been presented. This method was also found to work well for the synthesis of 1,4-oxazepane (Scheme 16). (For figures pl refer the abstract pdf file)