ETD Collection

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Author: search.filters.author.Mthembu, Siyanda ThabaniSubject: search.filters.subject.organic compounds

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    Enaminones in the synthesis of azabicyclic models for alkaloids
    (2008-10-06T13:36:45Z) Mthembu, Siyanda Thabani
    The purpose of this project was to investigate whether methodology developed in these laboratories for preparing 5/6 and 6/6 azabicyclic systems with bridged head nitrogen can be extended to 7/6, 8/6, 9/6 and 13/6 azabicyclic systems. The methodology entails the use of enaminones as central to the formation of the azabicyclic systems. The synthetic route adopted began with the Beckmann rearrangement reaction and/or the Schmidt reaction of cyclic ketones to make lactams, which were then thionated by Curphy or Brillon procedures. The Michael reaction of NH thiolactams with tert-butyl acrylate was followed by Eschenmoser sulfide contraction to afford the enaminones 132 which were utilised in the ring-closing step. This involved hydrolysis of the tert-butyl ester and cyclisation via a mixed anhydride. Ethyl 7-oxo-1,2,3,5,6,7-hexahydroindolizine-8-carboxylate 170b, 1-(4- nitrobenzoyl)-3,4,6,7,8,9-hexahydroquinolizin-2-one 172a, 1-benzoyl- 3,4,7,8,9,10-hexahydropyrido[1,2-a]azepin-2(6H)-one 173d, 1-(4-nitrobenzoyl)- 3,4,6,7,8,9,10,11-octahydropyrido[1,2-a]azocin-2-one 174a, and 1-(4- nitrobenzoyl)-3,4,7,8,9,10,11,12,13,14,17,16-dodecahydropyrido[1,2-a]azacyclotridecin- 2(6H)-one 176a were synthesised in good yields, but yields of 8-(4- nitrobenzoyl)-2,3,5,6-tetrahydroindolizin-7(1H)-one 171a and 1-(4-nitrobenzoyl)- 3,4,7,8,9,10,11,12-octahydropyrido[1,2-a]azonin-2(6H)-one 175a were not satisfactory. In a much shorter synthetic route that involves enaminone chemistry as well, NH vinylogous amides were synthesised by the Eschenmoser sulfide contraction and used in the aza-annulation reaction with acryloyl chloride. Structural isomers (to compounds mentioned above) 8-(4-nitrobenzoyl)-2,3,6,7-tetrahydroindolizin- 5(1H)-one 178a, 1-(4-nitrobenzoyl)-2,3,7,8,9,10-hexahydropyrido[1,2-a]azepin- 4(6H)-one 180a, 1-benzoyl-2,3,7,8,9,10-hexahydropyrido[1,2-a]azepin-4(6H)-one 180b, 1-(4-nitrobenzoyl)-2,3,6,7,8,9,10,11-octahydropyrido[1,2-a]azocin-4-one 181a, 1-(4-nitrobenzoyl)-2,3,7,8,9,10,11,12-octahydropyrido[1,2-a]azonin-4(6H)- one 182a and 1-(4-nitrobenzoyl)-2,6,7,8,9,10,11,12,13,14,15,16- dodecahydropyrido[1,2-a]azacyclo-tridecin-4(3H)-one 183a were synthesised in good yields. 1-(4-Nitrobenzoyl)-2,3,6,7,8,9-hexahydroquinolizin-4-one 179a was obtained in low yield, and apparently as two conformational isomers.