Synthesis of Substituted Bacteriochlorins

porphyrin;bacteriochlorin;chlorin

Meneely, Kelly Rose ; Christian Melander, Committee Member,Jonathan Lindsey, Committee Chair,Bruce Novak, Committee Member,Meneely, Kelly Rose ; Christian Melander ; Committee Member ; Jonathan Lindsey ; Committee Chair ; Bruce Novak ; Committee Member

University:North Carolina State University

关键词: porphyrin;    bacteriochlorin;    chlorin;   

Others  :  https://repository.lib.ncsu.edu/bitstream/handle/1840.16/6351/etd.pdf?sequence=1&isAllowed=y

美国|英语

来源: null

【 摘 要 】

The objective of this work is two-fold: first, to find new conditions to improve the condensation reactions leading to the macrocycles 3,13-dibromo-5-methoxybacteriochlorin (BC-Br3OMe5Br13) and 3,13-dibromobacteriochlorin (BC-Br3Br13), and second, to functionalize the valuable BC-Br3OMe5Br13 building block.This work improves upon past condensation methods, which afforded low yields of bacteriochlorin with an inseparable chlorin product during formation of BC-Br3Br13, and provided no access to BC-Br3OMe5Br13.Through microscale optimization of conditions, solvents, concentrations, Lewis acids, and additives, BC-Br3OMe5Br13 and BC-Br3Br13 were isolated in 42% and 30% yield, respectively. Several derivatizations including diacetylation of BC-Br3OMe5Br13 was achieved in 70% yield, followed by bromination at the β-position in 22% yield.Stille coupling of BC-Br3OMe5Br13 to introduce a formyl group was performed in 30% yield.Two TIPS-ethynyl groups were also installed on BC-Br3OMe5Br13 in 4.7% yield.