Research Projects

This proposal outlines the in situ generation of a novel class of metallocarbenes from the bicyclo[1,1,0]butanes (BCBs) using a ring-strain-enabled strategy in the presence of a transition-metal catalyst. Metallocarbenes are versatile synthons in organic chemistry, and their synthesis typically involves diazo compounds and related precursors in the presence of a transition-metal catalyst. However, these diazo compounds are highly explosive and toxic, and their precursors must be prepared before use, and their precursors require a multi-step synthesis process. To overcome these challenges, this proposal aims to achieve the diazo-free synthesis of metallocarbenes and generate a new class of metallocarbenes with two modifiable synthetic functional groups, which are important motifs in organic chemistry for the functional group interconversion. This innovative approach can potentially revolutionize the field of organic chemistry, providing a safer and more efficient method for metallocarbenes synthesis. In this proposal, Part-A deals with the synthesis of metallocarbenes and their functionalization for various transformations, such as intramolecular X–H insertion (X = C, O, NR, S), cyclopropanation, and other transformations for the synthesis of bicyclo[n,1,1]systems, fused bicyclic compounds, heterocyclic compounds via ring-strain enabled transformations, showcasing the versatility and potential impact of our proposed hypothesis. In Part-B, we proposed the generation of metallocarbenes from BCBs for intermolecular reactions in the presence of transition-metal catalysts. Using this methodology, one can easily access various tetrasubstituted carbonyl compounds, amides, and esters in a single step via rearrangement reactions like Doyle-Krimse, cyclopropanation, cyclopropenation, C–H, and X–H insertion reactions, among many other transformations. The present study thus aimed at providing new avenues for the non-diazo free generation of metallocarbenes from BCBs in organic synthesis. The reactions developed will find widespread applications in synthesizing bicyclo[n,1,1]systems, fused bicyclic compounds, heteroatom-containing small molecule therapeutics, building blocks, and biologically relevant natural products. This potential to revolutionize drug development is a testament to the transformative power of organic chemistry, inspiring hope for the future of pharmaceutical research.