Diastereo‐Divergent Synthesis of Saturated Azaheterocycles Enabled by tBuOK‐Mediated Hydroamination of Alkenyl Hydrazones |
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Authors: | Atsushi Kaga Dr Xingao Peng Prof?Dr Hajime Hirao Prof?Dr Shunsuke Chiba |
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Institution: | Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore) |
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Abstract: | Diastereo‐divergent synthesis of saturated azaheterocycles has been achieved by tBuOK‐mediated hydroamination of alkenyl hydrazones. DFT calculations suggested that the cation–π interactions between a potassium cation and aryl substituents on hydrazones give rise to 2,5‐cis selectivity in pyrrolidines, which were synthesized by the reaction of γ,δ‐unsaturated N‐benzyl hydrazones. By contrast, 2,5‐trans selectivity was observed when an isopropyl group was used as the substituent on hydrazones. An unusual 2,6‐trans selectivity in piperidine formation was also realized using the present strategy. |
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Keywords: | density functional calculations hydrazones hydroamination piperidines pyrrolidines |
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