Reductive dechlorination of amino-chlorobicycloalkanenitriles 5a-c was achieved by sodium in tert.butyl alkohol/THF to give the bicyclic nitriles 6a-c. LiAIH,, as dechlorination reagent caused a ring opening reaction with 5b,c producing diamines 7b,c. The bicyclic chloro compounds 5b,c could by obtained from enamines 1 via dichloroenamines 4. Monochlorination of 1 b,c and subsequent cyclopropanation with cyanide yielded endo-bicycloalkanenitriles 3b.c. Compounds 3 and 6 thus generally can be synthesized in a diastereocomplementary way starting from enamines 1.
Functionalized Chloroenamines in Aminocyclopropane Synthesis. Part 7.A Diastereocomplementary Approach to Aminobicyclo(n.1.0)alkanenitriles on the Basis of Chlorinated Enamines.-Chloroenamines (II) and (V) are selected as representative compounds to test the diastereoselectivity of the cyanide-induced cyclopropanation reaction. While (II) gives endo-bicycloalkanenitriles (III), the dichloroenamines (V) lead to an exo-morpholino system (VI), which is dechlorinated to give (VII), the exo isomers of (IV). The use of LiAlH4 as reductive agent causes ring opening of (VI) besides the expected reduction of the CN group. -(VILSMAIER, E.; STAMM, T.; DAUTH, W.; TETZLAFF, C.; BARTH, S.; Bull. Soc. Chim.
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