1-Nicotinoylbenzotriazole: A Convenient Tool for Site-Selective Protection of 5,7-Dihydroxycoumarins

Abstract

1-Nicotinoylbenzotriazole (NicBt) was uncovered as an efficient protecting agent for the site-selective acylation of resorcinol-type phenolic groups with almost equal reactivity. The use of NicBt allows selective protection of the 7-OH group in 5,7-dihydroxycoumarins in one simple scalable step, while combination of the nicotinoylation with tosylation–denicotinoylation or silylation–denicotinoylation yields 5-OH-protected 5,7-dihydroxycoumarins. Furthermore, nicotinoylated 5,7-dihydroxycoumarins proved useful in a gram-scale three-step preparation of a 2,2-dimethylpyrano[2,3-f]coumarin, a key intermediate for the synthesis of calanolide A, an HIV reverse transcriptase and Mycobacterium tuberculosis inhibitor, and its active analogues.

Key words

esterification - protecting groups - phenols - acylation - natural products - total synthesis

• References


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