Executive Summary : | After carefully studying the literature on DACPs and imino ketones, we found that very few reactions developed on the cyclization of DACPs with ambiphilic substrates containing both the nucleophile and electrophile centres. Further, there is not even a single report on the reaction of DACPs with imino ketones. Therefore, in this proposal, we would like to fill this gap to explore the new reactivities of these substrates towards their partners in furnishing the privileged molecules. The proposed reactions to be developed with the support of this grant are represented below in the form of six individual plans (schemes 9-17) with appropriate reaction mechanisms, wherever necessary. All the plans are interlinked from common precursors iminoketones and donor-acceptor cyclopropanes (DACPs). In the first Plan, we present a Friedel-Crafts arylation of imino ketone and a subsequent diastereoselective cyclization with donor-acceptor cyclopropanes (scheme 9). In the following Plan, we extend this to asymmetric FC-arylation (scheme 10). Thus, its diastereoselective cyclization with donor-acceptor cyclopropanes is proposed. Further, a probable logic for the diastereoselectivity based on a six-membered chair conformation is presented (scheme 11). In the 3rd Plan, we proposed ortho-C-H functionalization of N-phenyl anilines, followed by the in-situ preparation of imino ketones, FC-arylation and cyclization with DACPs (schemes 12-13). 4th Plan describes the inverse electron demand Diels-Alder (IEDA)cycloaddition of imino ketone followed by one-pot cyclization with DACPs (scheme 14). The 5th Plan is again an extension to plan 4. Here we use an exocyclic double bond for the inverse electron demand Diels-Alder (IEDA) cycloaddition to get spirocyclic of imino ketone, which follows a one-pot cyclization with DACP (schemes 15-16). The last Plan indicates our proposal to ortho-C-H functionalize N-phenyl anilines with terminal alkynes to get imino ketones, which are again in situ treated with DACPs (scheme 17). We have encouraging results under preliminary study towards FC-arylation reactions. |