Synthesis and Characterization of a Phosphorus – Based Olefin – Linked Porous Organic Polymer for Application as a Heterogeneous Support in Organic Synthesis

Kumar, Pramod (2024) Synthesis and Characterization of a Phosphorus – Based Olefin – Linked Porous Organic Polymer for Application as a Heterogeneous Support in Organic Synthesis. PhD thesis, Indian Institute of Science Education and Research Kolkata.

Text (PhD thesis of Pramod Kumar (18RS065)) 18RS065.pdf - Submitted Version Restricted to Repository staff only Download (20MB)

Abstract

Heterogeneous catalysis is evolving at an increasingly progressive rate. The prominent attribution to this growth lies in the reusability, robustness, separation, atom economy, and cost-effectiveness of the heterogeneous catalyst. It is noteworthy to mention that homogeneous catalysis has better activity and selectivity toward product formation. This effectiveness is mainly determined by the ligands used and in-built co-ordination sites. Strategically, phosphine has been incorporated here in a heterogeneous framework using Knoevenagel-type co-condensation protocol to harness the physicochemical properties of duo heterogeneous as well as homogeneous fields. The phosphine has been chosen as a coordination site because of its well-studied, strongly interacting nature with electrophiles in homogeneous catalysis. Concurrently, the Knoevenagel-type co-condensation solvothermal protocol has been carried forward to form a metal-free, strong olefin linkage to maintain the conjugation throughout the heterogeneous framework of PKPOP. Multiple control experiments have also been performed to focus on its morphological transformation from 2D sheet to 3D sphere. Further, PKPOP has been well characterized using various microscopic and spectroscopic instruments. Initially, the active site of this novel porous organic polymer has been exposed for the fixation of molecular iodine through iodination reaction via the formation of phosphonium ion. Later, the active nature of PKPOP encouraged further exposition of this framework for multi-component dicarbofunctionalization reaction after post-metalation with PdCl2 salt. During this application, multi-binding sites (P, CN, and olefin) supported in-situ formed Pd nanoparticles were well analyzed. Additionally, acquired knowledge of dicarbofunctionalization strategy in support of Pd nanoparticles embedded PKPOP was utilized for solving the issue of long-standing exclusive regio-selective indenone formation. This thesis discussed previous studies on phosphorus-containing porous organic polymers (P-POPs), their synthetic protocols, and their applications in organic reactions. After a thorough review of the literature, this thesis aimed to contribute further to the field of discussion via the synthesis of novel P-POP and its application in forming more synthetically challenging organic moieties.

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