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Investigation of the Corey Bromolactamization with N ‐Functionalized Allylamines
Author(s) -
Schulte Adrian,
Janich Simon,
Würthwein ErnstUlrich,
Saito Susumu,
Wünsch Bernhard
Publication year - 2016
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.2493
Subject(s) - chemistry , allylic rearrangement , yield (engineering) , glycine , carbamate , medicinal chemistry , organic chemistry , stereochemistry , catalysis , amino acid , biochemistry , materials science , metallurgy
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.