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Desaminierungsreaktionen, 52. Cyclopropandiazonium‐Ionen der [4.3.1] Propellan‐Reihe
Author(s) -
Kirmse Wolfgang,
Hellwig Georg
Publication year - 1989
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19891220232
Subject(s) - chemistry , carbocation , medicinal chemistry , amine gas treating , bicyclic molecule , bromide , deamination , nitrous acid , aqueous solution , lithium (medication) , solvolysis , delocalized electron , stereochemistry , organic chemistry , hydrolysis , medicine , enzyme , endocrinology
Deamination Reactions, 52. – Cyclopropanediazonium Ions Derived from [4.3.1] Propellanes Tricyclo[4.3.1.0. 1,6 ]dec‐3‐en‐10‐amines ( 16 , 17 ) and their saturated analogs ( 18 , 19 )were prepared by a multistep sequence, starting from ethyl 2‐oxo‐cyclopentanecarboxylate ( 8 ). The intermediate tricycol[4.3.1.0 1,6 ]dec‐3‐ene‐10‐carboxylic acids( 14 ) were separated and confugurationally assigned by iodolactonization of the synisomer. Nitrous acid deaminations of the amines 16–19 were performed in aqueous lithium bromide solutions. Thus, the intervening carbocations were trapped to give stable tricyclic bromides 23–26 as the major products. Predominant retention of configuration was observed with all substrates although the syn–amine 17 deviated significantly from its anti isomer 16 and from the higher homologs. Charge delocalization in the tricylic cation 31 appears to be enhanced relative to the bicyclo[3.1.0]hex‐3‐yl cation ( 3 ).