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Synthesis of highly functionalized 2,2'-bipyridines by cyclocondensation of β-ketoenamides - scope and limitations.

ABSTRACT: The scope of a flexible route to unsymmetrically functionalized bipyridines is described. Starting from 1,3-diketones 1a-e, the corresponding β-ketoenamines 2a-e were converted into different β-ketoenamides 3a-g by N-acylation with 2-pyridinecarboxylic acid derivatives. These β-ketoenamides were treated with a mixture of TMSOTf and Hünig's base to promote the cyclocondensation to 4-hydroxypyridine derivatives. Their immediate O-nonaflation employing nonafluorobutanesulfonyl fluoride provided the expected 4-nonafloxy-substituted bipyridine derivatives 5a-g in moderate to good overall yields. The bipyridyl nonaflates are excellent precursors for palladium-catalyzed reactions as demonstrated by representative Suzuki and Sonogashira couplings. Thus, a library of specifically substituted bipyridine derivatives was generated, showing the versatility of the simple 1,3-diketone-based approach to this important class of ligands.

SUBMITTER: Hommes P

PROVIDER: S-EPMC4979911 | biostudies-literature | 2016

REPOSITORIES: biostudies-literature

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Synthesis of highly functionalized 2,2'-bipyridines by cyclocondensation of β-ketoenamides - scope and limitations.

Hommes Paul P Reissig Hans-Ulrich HU

Beilstein journal of organic chemistry 20160609

The scope of a flexible route to unsymmetrically functionalized bipyridines is described. Starting from 1,3-diketones 1a-e, the corresponding β-ketoenamines 2a-e were converted into different β-ketoenamides 3a-g by N-acylation with 2-pyridinecarboxylic acid derivatives. These β-ketoenamides were treated with a mixture of TMSOTf and Hünig's base to promote the cyclocondensation to 4-hydroxypyridine derivatives. Their immediate O-nonaflation employing nonafluorobutanesulfonyl fluoride provided the ...[more]

PMID: 27559368

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