Synthesis and Reactivity of Anthracene-Based Molecular Precursors for Low-Valent Boron Species
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Sukhram-dions-bs-chemistry-2023-thesis.pdf
Description
Thesis PDF
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14.7 MB
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Adobe PDF
Checksum (MD5)
cd04289b73d9bcd3b4731a45e09c6c23
Author(s)
Sukhram, Dion S.
Advisor(s)
Cummins, Christopher C.
Date Issued
June 2023
Publisher
Massachusetts Institute of Technology
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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