N-phenyl-substituted pyrrolidines, piperidines and azabicyclics by a tandem reduction-double reductive amination reaction
N-phenyl-substituted pyrrolidines, piperidines and azabicyclics by a tandem reduction-double reductive amination reaction
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DOI：
10.1002/jhet.5570400115
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发表时间：
2003-01-01
影响因子：
2.4
通讯作者：
Kotturi, SV
中科院分区：
文献类型：
--
作者：
Bunce, RA;Herron, DM;Kotturi, SV
N-苯基取代的吡咯烷和哌啶分别通过硝基苯在4-和5-氧代醛存在下催化还原来合成。该方法包括还原芳族硝基，得到 N-苯基羟胺或苯胺，然后用两个羰基官能团进行还原胺化。单环系统通常以高产率形成并且易于纯化。该方法还扩展到从 2-(3-氧代丙基)环烷酮合成稠合 N-苯基氮杂双环。在环烷酮羰基具有酯基α的底物中观察到转稠合产物的高度非对映选择性。缺乏该酯基的双环前体产生顺式和反式产物的混合物。最后，与之前的报道相反，我们证明在这些反应中苯胺可以取代硝基苯。
N-Phenyl-substituted pyrrolidines and piperidines have been synthesized by catalytic reduction of nitrobenzene in the presence of 4- and 5-oxoaldehydes, respectively. The process involves reduction of the aromatic nitro group to give the N-phenylhydroxylamine or aniline followed by reductive amination with the two carbonyl functional groups. Monocyclic systems are generally formed in high yield and are easily purified. The method has also been extended to the synthesis of fused N-phenylazabicyclics from 2-(3-oxopropyl)cycloalkanones. A high degree of diastereoselectivity for the trans-fused product is observed in substrates having an ester group a to the cycloalkanone carbonyl. Bicyclic precursors lacking this ester group give mixtures of cis and trans products. Finally, contrary to previous reports, we have demonstrated that aniline can be substituted for nitrobenzene in these reactions.