Takemiya Akihiro, Hartwig John F
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
J Am Chem Soc. 2006 May 10;128(18):6042-3. doi: 10.1021/ja058299e.
The intramolecular anti-Markovnikov hydroamination of 1-(3-aminopropyl)vinylarenes in the presence of a readily available rhodium catalyst to form 3-arylpiperidines is reported. In contrast to intermolecular hydroamination of vinylarenes, which occurred in high yields in the presence of rhodium catalysts containing DPEphos, the intramolecular reaction occurred in high yield in the presence of [Rh(COD)(DPPB)]BF4 as catalyst. Reactants with substituents beta to the nitrogen occurred in high yield, and these reactions formed 3,5-disubstituted piperidines with high diastereomeric excess. The regiochemistry of these cyclizations contrasts with the regiochemistry of intramolecular hydroaminations catalyzed by lanthanide complexes, group III metal complexes, and platinum complexes, all of which have been reported to form cyclization products from Markovnikov addition.
据报道，在一种易于获得的铑催化剂存在下，1-(3-氨基丙基)乙烯基芳烃发生分子内反马氏氢胺化反应，生成3-芳基哌啶。与乙烯基芳烃的分子间氢胺化反应不同，后者在含有DPEphos的铑催化剂存在下能高产率发生，而分子内反应在[Rh(COD)(DPPB)]BF4作为催化剂存在下高产率发生。氮原子β位带有取代基的反应物能高产率反应，且这些反应生成具有高非对映体过量的3,5-二取代哌啶。这些环化反应的区域化学与镧系配合物、Ⅲ族金属配合物和铂配合物催化的分子内氢胺化反应的区域化学形成对比，据报道，所有这些配合物催化的反应均通过马氏加成形成环化产物。
