Research Projects

This study explores carbene and carbyne precursors for novel organic transformations. Alkynyl diazo compounds are under explored carbene surrogates and merely limited to simple carbene transfer reactions. Though the alkyne functional group is an excellent synthetic handle, it was untouched in these transformations. Importantly, developing such a research domain and merging it with asymmetric catalysis could unlock entirely new avenues for the synthesis of enantioenriched target-oriented molecules. The monovalent carbyne has the potential for multi-functionalization at a single point assembly and forms three new bonds by reacting with two nucleophiles and an electrophile. Such developments are limited to acceptor-type carbynes and activation of traditional imine precursors. Herein, we design novel donor-type carbyne precursors with an intention to utilize them in new catalytic modes and skeletal editing problems. The objective of the project is to design and develop tunable carbene and carbyne precursors and harnessing their reactivity under mild reaction conditions. The dual reactivity of carbene and alkyne in alkynyl diazo compounds is targeted towards delivering that molecular scaffolds are challenging to obtain via conventional methodologies. The carbyne precursors will be employed for asymmetric transformations via metal-carbynoid chemistry. Also, pharmaceutically important N-heterocycles will be synthesized under metal-free photochemical conditions. This proposal seeks to understand fundamental mechanistic aspects of carbene- and carbyne-mediated transformations, with an objective of facilitating the rational design for new developments. We aim to investigate the cascade chemistry of alkynes via an enantioselective alkynyl carboxylate carbene transfer reactions. We hypothesize that the carboxylate-substituted propargyl center can easily be isomerized to activated allenoates under base catalysis. The rich chemistry of allenoates can further be explored for the enantioselective synthesis of: a) indoline-fused cyclobutane and cyclobutene scaffolds via carbene insertion into N-H bonds of alkenyl anilines and dynamic kinetic resolution of propargylamines; b) furan-fused carbocycles via asymmetric insertion of carbenes into O-H bonds of 2-furfuryl alcohol, base-promoted isomerization, [4+2] cycloaddition and ring-opening cascade; and c) tetrasubstituted vinyl haloallenes via halide addition to an electrophilic enynyl carbene and regioselective trapping of an electrophile. On the other hand, alkynyl carbyne species will be generated through synthesis and decomposition of the corresponding hypervalent iodine(III) diazo compounds. The donor-type monovalent carbynes will be utilized for enantioselective multi-functionalization and skeletal editing of N-heterocycles (pyrrole, indoles, and Troger base, etc.) under metal catalyzed and metal-free photochemical conditions. If successful, the research will transform the toolkit available for constructing architecturally complex, stereochemically rich molecules—particularly those valuable in medicinal chemistry and materials science. By enabling unprecedented selective transformations and late-stage molecular editing, these advances could streamline the synthesis of high-value compounds and unveil new paradigms for asymmetric catalysis. Mechanistic understanding gained from these studies will not only deepen fundamental knowledge of reactive intermediates but also foster innovation in the design of next-generation catalysts and reaction platforms. Ultimately, this project stands to bridge significant gaps in synthetic methodology, empowering the field to access and modify molecular frameworks previously considered unattainable.