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Aminoreduktone – Untersuchungen an Verbindungen mit dem C‐Gerüst des Dimedons und mit sekundären Aminen als Bausteinen
Author(s) -
Schank Kurt,
Glock Rebecca,
Lick Carlo
Publication year - 2005
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200590256
Subject(s) - chemistry , aminolysis , autoxidation , regioselectivity , medicinal chemistry , oxidizing agent , ring (chemistry) , stereochemistry , organic chemistry , catalysis
Aminoreductones – Investigations on Species Containing the Carbon Arrangement of Dimedone and Secondary Amines as Building Blocks The ozonation of 3‐( sec ‐amino)‐5,5‐dimethylcyclohex‐2‐en‐1‐ones 4 was compared with the corresponding acyloxylations by diacylperoxides 5 , making accessible 3‐( sec ‐amino)‐reductones 9 . Both types of oxygenation also led to higher‐oxygenated six‐ring carbocyclic products ( 7, 8, 17 ), ozonation being a minor reaction path, in addition to CC cleavage. The corresponding 2‐( sec ‐amino)reductones 34 were generated via aminolysis of the iodonium intermediate 44 ( Scheme 13 ), and their reductive behavior against t ‐BuOCl and 3‐chloroperbenzoic acid (MCPBA) as oxidizing agents was compared. Attempts to generate the corresponding reductone 5,5‐dimethyl‐2,3‐dimorpholin‐4‐ylcyclohex‐2‐en‐1‐one ( 45 ) were unsuccessful ( Scheme 13 ). Instead, the corresponding iodonium intermediate 44 suffered a Favorskii ‐like regioselective ring contraction during aminolysis, followed by autoxidation. These unexpected reactions were confirmed by separate experiments.