Title:
Ring-opening benzannulations of cyclopropenes, alkylidene cyclopropanes, and 2,3-dihydrofuran acetals: A complementary approach to benzo-fused (hetero)aromatics
Ring-opening benzannulations of cyclopropenes, alkylidene cyclopropanes, and 2,3-dihydrofuran acetals: A complementary approach to benzo-fused (hetero)aromatics
Author(s)
Aponte-Guzman, Joel
Advisor(s)
France, Stefan
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Abstract
Over the past decades, functional group manipulation of aromatic precursors has been a common strategy to access new aromatic compounds. However, these classical methods, such as Friedel-Crafts alkylations and electrophilic/nucleophilic aromatic substitutions, have shown lack of regioselectivity besides the use of activators in excess amounts. To this end, numerous benzannulations to form benzo-fused substrates via Diels-Alder (DA), ring-closing metathesis (RCM), cycloaddition, and transition-metal-promoted processes have been reported. Appending a benzene ring directly onto a pre-existing ring is preferable to many classical methods due to the likely reduction of reaction steps and superior regiocontrol. However, many of these benzannulation reactions require air- and/or moisture- sensitive reaction conditions, a last oxidation step, or the use of highly functionalized precursors. Here we disclose three ‘complementary’ intramolecular ring-opening benzannulations to access a large array of functionalized (hetero)aromatic scaffolds utilizing cyclopropenes-3,3-dicarbonyls, alkylidene cyclopropanes-1,1-diesters, and 2,3-dihydrofuran O,O- and N,O- acetals as building blocks. More than 70 benzo-fused aromatic compounds were synthesized using this complementary approach with yields up to 98% and low catalyst loadings. With these benzannulation reactions in hand, we aim to open the synthetic door to a handful of bioactive natural products.
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Date Issued
2016-05-27
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Text
Resource Subtype
Dissertation