Investigation of the Corey Bromolactamization with N‐Functionalized Allylamines |
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| Authors: | Adrian Schulte Simon Janich Ernst‐Ulrich Würthwein Susumu Saito Bernhard Wünsch |
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| Institution: | 1. Institut für Pharmazeutische und Medizinische Chemie, Westf?lische Wilhelms‐Universit?t Münster, Münster, Germany;2. Organisch‐Chemisches Institut, Westf?lische Wilhelms‐Universit?t Münster, Münster, Germany;3. Research Center for Materials Science, Nagoya University, Nagoya, Japan;4. Cells‐in‐Motion Cluster of Excellence (EXC 1003‐CiM), Westf?lische Wilhelms‐Universit?t Münster, Münster, Germany |
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| Abstract: | N‐Allylamines were employed for the diastereoselective synthesis of
8‐bromo‐substituted, cis‐configured perhydroquinoxalines and β‐bromoalcohols. The yield and constitution of the products depend considerably on the functionalization of the allylic N‐atom. Herein the reaction of glycine‐derived cyclohex‐2‐enamines 5 under bromolactamization conditions (LiOtBu, NBS) is reported. Methyl carbamate 5a led diastereoselectively to the cis‐configured perhydroquinoxaline 6a , whereas the amides 5b and 5c provided cis,trans‐configured ‐bromoalcohols 7b and 7c . Based on high level theoretical calculations (DFT) factors controlling the cyclization of lithiated intermediates and the relative energies of possible products are discussed. |
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