Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
10569618 | Coordination Chemistry Reviews | 2013 | 22 Pages |
Abstract
⺠Approach to periphery modification centered on the application of diradicals generated through unique diyne-ene and diazo-keto functionalization at the β,βâ²-position of the macrocycle. ⺠Diradical adds across the adjacent phenyl rings of the meso-positions to extend the aromaticity across three rings. ⺠Dione or diazo-keto functionalization and subsequent reaction with nucleophiles in the presence of Ag+, generates acetals that lead to modified chemical properties additional reactivity potential at the periphery - diazoketochlorin photolysis leads to rapid N2 extrusion and initial carbene formation. ⺠Wolff ring-contracted ketene, is detectable, demonstrating that the out-of-plane electronic configuration is initially generated and reacts to give the nucleophile-quenched species, as well as relaxing to form exocyclic ring addition and other radical-based products. ⺠Synthetic opportunities to markedly modulate macrocycle electronic structure in a highly asymmetric manner to form truly distinct porphyrinoid constructs.
Related Topics
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Authors
Leigh J.K. Boerner, David. F. Dye, Tillmann Köpke, Jeffrey M. Zaleski,