2026-09-20T18:07:07Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/1521292023-09-14T03:40:40Zcom_1721.1_7582com_1721.1_7581col_1721.1_131024
Cummins, Christopher C.
Sukhram, Dion S.
Massachusetts Institute of Technology. Department of Chemistry
2023-09-13T18:07:13Z
2023-09-13T18:07:13Z
2023-06
2023-09-05T20:09:24.926Z
https://hdl.handle.net/1721.1/152129
0009-0009-6381-7118
The study of compounds containing elusive main group multiple bonds has long been a topic of immense interest. Today, it remains an attractive path towards unlocking new reactivity and developing a complete empirical understanding of chemical bonding. However, due in large part to a lack of suitable synthetic methodologies, the chemistry of numerous desirable functionalities remains poorly accessible. Herein, we report the synthesis of the first series of dibenzo-7-boranorbornadienes, or 9,10-bridged boron anthracene (RBA, A = anthracene or C₁₄H₁₀) compounds, and their unique properties and reactivity. Oxidation of ⁱPr₂NBA with an amine oxide was found to lead to the selective formation of the bicyclic borinate ester ⁱPr₂NBOA, an easily isolable solid that unimolecularly fragments to ⁱPr₂NBO + A upon heating to moderate temperatures in solution. This rare free, monomeric oxoborane has been demonstrated to undergo cycloadditions with a number of organic substrates and efforts to expand both the scope of derivatives and reactivity are underway. The possibility to access species containing highly unstable boron-pnictogen triple bonds has also been explored via the synthesis of the azidoborane trimer (N₃BA)₃ and cyclic(alkyl)(amino)carbene (CAAC) stabilized boraphosphaketene ᵉᵗCAAC·ABPCO. Preliminary and ongoing reactivity studies are discussed.
S.B.
Massachusetts Institute of Technology
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Synthesis and Reactivity of Anthracene-Based Molecular Precursors for Low-Valent Boron Species
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Bachelor of Science in Chemistry
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<Abstract>The study of compounds containing elusive main group multiple bonds has long been a topic of immense interest. Today, it remains an attractive path towards unlocking new reactivity and developing a complete empirical understanding of chemical bonding. However, due in large part to a lack of suitable synthetic methodologies, the chemistry of numerous desirable functionalities remains poorly accessible. Herein, we report the synthesis of the first series of dibenzo-7-boranorbornadienes, or 9,10-bridged boron anthracene (RBA, A = anthracene or C₁₄H₁₀) compounds, and their unique properties and reactivity. Oxidation of ⁱPr₂NBA with an amine oxide was found to lead to the selective formation of the bicyclic borinate ester ⁱPr₂NBOA, an easily isolable solid that unimolecularly fragments to ⁱPr₂NBO + A upon heating to moderate temperatures in solution. This rare free, monomeric oxoborane has been demonstrated to undergo cycloadditions with a number of organic substrates and efforts to expand both the scope of derivatives and reactivity are underway. The possibility to access species containing highly unstable boron-pnictogen triple bonds has also been explored via the synthesis of the azidoborane trimer (N₃BA)₃ and cyclic(alkyl)(amino)carbene (CAAC) stabilized boraphosphaketene ᵉᵗCAAC·ABPCO. Preliminary and ongoing reactivity studies are discussed.</Abstract>
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