jo990041h_si_001.pdf (846.67 kB)
Hydrolysis of Iminium Ethers Derived from the Reaction of Ketones with Hydroxy Azides: Synthesis of Macrocyclic Lactams and Lactones
journal contribution
posted on 1999-05-15, 00:00 authored by Jennifer E. Forsee, Jeffrey AubéThe hydrolysis of iminium ether intermediates formed by a nitrogen insertion sequence involving
azido alcohols 1 or 2 and ketones was investigated. Ketones containing 6−12-membered rings were
surveyed and shown to provide lactams and lactones in good to excellent overall yield. Reactions
employing acetone or 5-nonanone gave similar results, generating analogous amides and esters.
The relative amounts of lactone vs lactam produced in a given reaction were found to depend on
the structures of the reactants and the pH of the basic media used to hydrolyze the iminium ethers.
A mechanism accounting for the formation of each product is discussed in terms of ring strain and
the protonation state of ortho ester aminal intermediates.
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estersazido alcohols 1Azideortho ester aminal intermediatesnonanonereactantsring strainiminium ethersLactonelactone vs lactammechanism accountingHydrolysiiminium ether intermediatesnitrogen insertion sequenceprotonation stateMacrocyclic LactamshydrolyzepHSynthesiKetoneformationHydroxyacetoneIminium Ethers Derivedamidehydrolysisketonemembered
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