Recyclable λ3-iodanes for the generation of enolonium and dienolonium species and their synthetic applications
Implementing Organization
Sreenidhi University
Principal Investigator
Dr. Keshaba Nanda Parida
Sreenidhi University
pkeshaba@niuniv.com
Project Overview
Installation of novel bonds based on ionic chemistry is the addition of oppositely charged centers, i.e., a nucleophile, aka donor “d”, with an electrophile, aka acceptor, “a”. The bond formation between two species of identical charges is classically not possible. The umpolung, i.e., polarity reversal, of enolate, a d2 synthon, can offer an a2 synthon. We generate such an electron deficient species from the reaction of ketone or enolate and hypervalent iodine compounds. The protocol allowed Carbon Carbon and Carbon heteroatom bond constructions, and gave access to several compounds like gamma, delta-unsaturated ketones, alpha- heteroarylketones, gamma-diketones, alpha-aryl-alpha,beta-unsaturated ketones, etc. However, the protocol has demerits like very low operation temperatures minus 78 degree C, highly acidic conditions, internal competitive nucleophiles like tosylate, recyclability, etc. I propose to develop novel recyclable lambda-3 iodanes with poorly nucleophilic fluoride ligands, the in-situ generation of enolonium from these compounds will selectively permit the addition of external nucleophiles. With a long fluoroalkyl chain, the iodanes will be soluble in a common organic solvent; the use of acid additives can be avoided. An introduction of Me group ortho to iodine in lambda3 iodane will enhance reactivity and solubility. Polymer-supported recyclable hypervalent iodine compounds with fluoride counter anion will be very useful for the application. I intend to generate an unprecedented dienolonium species from beta,gamma-unsaturated ketones, which will have vast applicability. I am also working on molecular electronics, where organic molecules with easy turnability, accessibility and processability, and cost-effectiveness can replace silicon-based semiconductors. For further miniaturization of the dimension of electronics, the development of a nano-level or even smaller-dimension scaffold is required. We are studying novel organic molecules in between junctions, where the nano-gap is practically a molecule within 0.5 to 1.5 nm. I have collaborated with Dr. Veerabhadra, IISc Bangalore, and Dr. Jerry, Ferriero, IISER Thiruvananthapuram. The research is at a primitive stage in India, and it will be a breakthrough for the development of next-generation organic electronics.