Mild Stereoselective Intermolecular Acetoxylation and Azidation of α-C−H Bonds in Tröger's Bases
Introduction of oxygen and nitrogen into organic molecules is one of the fundamental strategies for their functionalization. Traditional approaches rely on the formation of an activated intermediate, which is then modified in a subsequent step. Here we report a simple direct oxidative α‐acetoxylatio...
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| Veröffentlicht in: | Advanced synthesis & catalysis 2016-09, Vol.358 (17), p.2739-2744 |
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| container_end_page | 2744 |
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| container_issue | 17 |
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| container_title | Advanced synthesis & catalysis |
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| creator | Pereira, Raul Ondrisek, Pavol Kubincová, Alžbeta Otth, Elisabeth Cvengroš, Ján |
| description | Introduction of oxygen and nitrogen into organic molecules is one of the fundamental strategies for their functionalization. Traditional approaches rely on the formation of an activated intermediate, which is then modified in a subsequent step. Here we report a simple direct oxidative α‐acetoxylation and azidation of α‐C−H bonds in Tröger's base analogues promoted by N‐bromosuccinimide (NBS) and palladium(II)acetate [Pd(OAc)2] under mild conditions. This approach is pivotal on NBS oxidizing the carbon atoms next to the nitrogen atoms in the presence of Pd(OAc)2 followed by a reaction with oxygen‐ or nitrogen‐centred nucleophiles such as KOAc or NaN3 to yield either the mono‐ and bisacetoxylated or azidated Tröger's base derivatives in a stereo‐ and chemoselective manner. The obtained products can be efficiently modified to access synthetically meaningful structures. |
| doi_str_mv | 10.1002/adsc.201600415 |
| format | Article |
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Traditional approaches rely on the formation of an activated intermediate, which is then modified in a subsequent step. Here we report a simple direct oxidative α‐acetoxylation and azidation of α‐C−H bonds in Tröger's base analogues promoted by N‐bromosuccinimide (NBS) and palladium(II)acetate [Pd(OAc)2] under mild conditions. This approach is pivotal on NBS oxidizing the carbon atoms next to the nitrogen atoms in the presence of Pd(OAc)2 followed by a reaction with oxygen‐ or nitrogen‐centred nucleophiles such as KOAc or NaN3 to yield either the mono‐ and bisacetoxylated or azidated Tröger's base derivatives in a stereo‐ and chemoselective manner. 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| ispartof | Advanced synthesis & catalysis, 2016-09, Vol.358 (17), p.2739-2744 |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | acetoxylation azidation Carbon Chemical bonds C−H functionalization Derivatives Molecular chains Nitrogen Nitrogen atoms Nucleophiles Organic chemistry Oxidation Palladium Sodium azides Strategy Tröger's base |
| title | Mild Stereoselective Intermolecular Acetoxylation and Azidation of α-C−H Bonds in Tröger's Bases |
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