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Volumn 74, Issue 4, 2009, Pages 1567-1573

Synthetic studies on N-alkoxyamines: A mild and broadly applicable route starting from nitroxide radicals and aldehydes

Author keywords

[No Author keywords available]

Indexed keywords

ALKOXYAMINES; FRAGMENTATION REACTIONS; GOOD YIELDS; NITROXIDE RADICALS; SYNTHETIC STUDIES;

EID: 64349095050     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo802403j     Document Type: Article
Times cited : (42)

References (57)
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    • Commercial Product of Ciba Inc
    • Commercial Product of Ciba Inc.
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    • The same reactions were also conducted with TEMPO, but because of limited options for further chemical transformations this nitroxide radical is of little use in industrial applications
    • The same reactions were also conducted with TEMPO, but because of limited options for further chemical transformations this nitroxide radical is of little use in industrial applications.
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    • Alkoxyamines based on the 2,6-diethyl-4-hydroxy-2,3,6-trimethylpip- eridine-1-N-oxyl core were also prepared. As a result of the higher sterical hindrance, prolonged reaction times were observed.
    • Alkoxyamines based on the 2,6-diethyl-4-hydroxy-2,3,6-trimethylpip- eridine-1-N-oxyl core were also prepared. As a result of the higher sterical hindrance, prolonged reaction times were observed.
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    • Typical byproducts ofthis process were 4-oxo-alkoxyamines and C-1- shortened carbon chain homologues of the respective products in small amounts. The former ones can be transformed into the desired product by means of a sodium borohydride treatment during the workup process; the latter ones usually do not have a negative impact on subsequent chemistry. In addition, 1-hydroxy- 2,2,6,6-tetramethyl-4-piperidinol and 2-methyl-2-penten-4-one were formed and were removed during the workup process. Among the gaseous byproducts carbon dioxide and, in some cases, olefins (generated via β-H radical elimination of the respective alkyl radicals) were identified by GC-MS.
    • Typical byproducts ofthis process were 4-oxo-alkoxyamines and C-1- shortened carbon chain homologues of the respective products in small amounts. The former ones can be transformed into the desired product by means of a sodium borohydride treatment during the workup process; the latter ones usually do not have a negative impact on subsequent chemistry. In addition, 1-hydroxy- 2,2,6,6-tetramethyl-4-piperidinol and 2-methyl-2-penten-4-one were formed and were removed during the workup process. Among the gaseous byproducts carbon dioxide and, in some cases, olefins (generated via β-H radical elimination of the respective alkyl radicals) were identified by GC-MS.


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