Generation of endo- and/or exo-norbornenecarboxaldehyde as an intermediate to functionalized norbornenes

Abstract

Embodiments in accordance with the present invention provide for forming essentially pure diastereomers of 5/6-substituted norbornene-type monomers. Further, embodiments in accordance with the present invention encompass polymerizing such diastereomers to form addition or ROMP polymers where a desired exo-/endo-ratio of the diastereomers is provided to the polymerization, such ratio designed to provide a desired ratio of endo-/exo-structured repeating units for a resulting polymer to have desired physical or chemical properties.

1 . A method for forming essentially pure exo- and/or endo-substituted polycyclic olefin monomers, comprising:
 forming a diastereomeric mixture of norbornenecarbonitrile (NBCN) via a Diels-Alder reaction;   separating the endo- and exo-diastereomers of such diastereomeric mixture;   selecting one of the exo- or endo-diastereomers and contacting such selected diastereomer with cyclopentadiene to form the selected tetracyclododecenecarbonitrile (TDCN);   first converting such selected TDCN to a tetracyclododecenecarbaldehyde (TDCHO); and   second converting the TDCHO to one of a tetracyclododecene carboxylic acid (TDCO 2 H) or a tetracyclododecene methyl alcohol (TDCH 2 OH).   
   
   
       2 . The method of  claim 1 , where selecting comprises selecting the exo-diastereomer. 
   
   
       3 . The method of  claim 1 , where the first converting comprises charging a reaction vessel with a metal hydride and the selected TDCN diastereomer to effect a reduction of such TDCN diastereomer and subsequently hydrolysing the reaction intermediate. 
   
   
       4 . The method of  claim 1 , where the second converting comprises charging a reaction vessel with a hydride donor reagent and an individual exo- or endo-carboaldehyde containing diastereomer to effect a reduction of the exo- or endo-carboaldehyde containing diastereomer. 
   
   
       5 . The method of  claim 1 , where the second converting comprises charging a reaction vessel with an appropriate oxidizing agent and an individual exo- or endo-carboaldehyde containing diastereomer to effect an oxidation of the exo- or endo-carboaldehyde containing diastereomer. 
   
   
       6 . The method of  claim 3 , where the second converting comprises charging a reaction vessel with an appropriate oxidizing agent and an individual exo- or endo-carboaldehyde containing diastereomer to effect an oxidation of the exo- or endo-carboaldehyde containing diastereomer. 
   
   
       7 . The method of  claim 3 , where the second converting comprises charging a reaction vessel with an appropriate reducing agent and an individual exo- or endo-carboaldehyde containing diastereomer to effect a reduction of the exo- or endo-carboaldehyde containing diastereomer. 
   
   
       8 . The method of  claim 3 , where the second converting comprises charging a reaction vessel with a hydride donor reagent and an individual exo- or endo-carboaldehyde containing diastereomer to effect a reduction of the exo- or endo-carboaldehyde containing diastereomer. 
   
   
       9 . The method of  claim 3 , where the metal hydride comprises lithium aluminum hydride, alkyl aluminum hydrides, alkoxyaluminum hydrides, or dialkylamino lithium hydrides.