β-氨基Weinreb酰胺的不对称合成及其应用：（S）-coniine的不对称合成。
Asymmetric synthesis and applications of beta-amino Weinreb amides: asymmetric synthesis of (S)-coniine.
作者信息
Burke Anthony J, Davies Stephen G, Garner A Christopher, McCarthy Tom D, Roberts Paul M, Smith Andrew D, Rodriguez-Solla Humberto, Vickers Richard J
机构信息
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, UK OX1 3TA.
出版信息
Org Biomol Chem. 2004 May 7;2(9):1387-94. doi: 10.1039/b402531h. Epub 2004 Apr 5.
Conjugate addition of lithium (S)-N-benzyl-N-alpha-methylbenzylamide to a range of alpha, beta-unsaturated Weinreb amides proceeds with high levels of diastereoselectivity (>95% de). The beta-amino Weinreb amide products may be transformed into beta-amino ketones via reactions with Grignard reagents, while treatment with DIBAL-H furnishes beta-amino aldehydes. Trapping of the aldehyde via Wadsworth-Emmons reaction and subsequent manipulation offers an efficient route to homochiral delta-amino acid derivatives and 2-substituted piperidines. The application of this methodology for the synthesis of (S)-coniine is demonstrated.
将锂（S）-N-苄基-N-α-甲基苄基酰胺与一系列α，β-不饱和Weinreb酰胺进行共轭加成反应，具有高非对映选择性（>95%的非对映体过量）。β-氨基Weinreb酰胺产物可通过与格氏试剂反应转化为β-氨基酮，而用二异丁基氢化铝（DIBAL-H）处理则得到β-氨基醛。通过Wadsworth-Emmons反应捕获醛并随后进行操作，为合成手性δ-氨基酸衍生物和2-取代哌啶提供了一条有效途径。展示了该方法在合成（S）-coniine中的应用。
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