Unconventional Umpolung of Bromocations in the Accelerated Organocatalytic Dibromination of C⚌C/C≡C Bonds Alongside Kinetic Studies to Establish the Structure-Reactivity Relationship of C⚌C Bonds

Panda, Jeetendra (2024) Unconventional Umpolung of Bromocations in the Accelerated Organocatalytic Dibromination of C⚌C/C≡C Bonds Alongside Kinetic Studies to Establish the Structure-Reactivity Relationship of C⚌C Bonds. PhD thesis.

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Abstract

Chapter 1. A Short Review on Umpolung Strategy: Advances in new chemical bond Formation This chapter gives an overview of umpolung activity of carbon atoms alongwith rarely reported polarity reversal of halogens. Additionally, it gives concise information about organocatalytic dibromination of C—C unsaturated bonds. Chapter 2. Study Towards Organocatalyzed Umpolung of Bromocation Species An elaborate investigation into the umpolung of the never reported bromocationic source has been addressed. In this chapter a detailed study of the interaction of various halogen sources with amine catalyst has been discussed. Furthermore, the pole reversal of the bromocations has been well supported by the experimental and computational evidences. Chapter 3. Accelerated Organocatalytic Dibromination of Unsaturated C-C bonds In this chapter, the elaborated protocol paved the way for the direct syntheses of the dibromo compounds using the polarity reversal technique, which was achieved tactically in-situ and catalytically by employing simple amine organocatalysts. This environment benign methodology would be an alternate for the age old methods of dibromination. Chapter 4. Structure-Reactivity relationship of olefins as Electrophiles and Nucleophiles: Factors Influencing In this short study we have shown real-time experiments of how the reactivity of the olefins varies when the electron density over the olefinic bond is varied. Also, it has been showcased how the planar orientation of the olefin could nullify these substitution effects. Chapter 5. Effort Towards Synthesis of Chiral N-Halosuccinimides: Potential Reagents for Asymmetric Cohalogenation Transformations In this chapter, an effort towards synthesis of chiral NBS was achieved until the N-protected imide with good to excellent yields. Although there are some challenges in the deprotection of the N-protected imides, but optimization of the deprotection is currently undergoing in our laboratory. Additionally, a successful mimicking synthetic procedure has been developed for the bromination of imides to N-bromo imides. Chapter 6. Conclusion and Future Scope In the last chapter, the present work's overall summary and future scopes have been Described.

Item Type:Thesis (PhD)
Uncontrolled Keywords:Electrophilic bromination; C⚌C bond functionalization; Organocatalysis; Alkene dibromination; Dibromination; Reaction acceleration; Alkyne dibromination; Catalytic halogenation; Umpolung; Kinetic studies; Bromocations
Subjects:Chemistry > Organic Chemistry
Chemistry > Pharmaceutical Chemistry
Divisions: Sciences > Department of Chemistry
ID Code:10707
Deposited By:IR Staff BPCL
Deposited On:02 Sep 2025 13:07
Last Modified:02 Sep 2025 13:07
Supervisor(s):Sahoo, Gokarneswar

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