PartI. Study of 1-Acyl-2-dimethylphenylsilyl-2,3-dihydro-4-pyridone as Synthetic Intermediates.Part II. Synthesis of Nicotine Derivatives from Nicotine.

dihydropyridine;dihydropyridone;3-dihydro-4-pyridone;1-acyl-2-dimethylphenylsilyl-2;nicotine derivatives;dihydronicotine

Smith, Emilie Despagnet ; Daniel L. Comins, Committee Chair,Smith, Emilie Despagnet ; Daniel L. Comins ; Committee Chair

University:North Carolina State University

关键词: dihydropyridine;    dihydropyridone;    3-dihydro-4-pyridone;    1-acyl-2-dimethylphenylsilyl-2;    nicotine derivatives;    dihydronicotine;   

Others  :  https://repository.lib.ncsu.edu/bitstream/handle/1840.16/3744/etd.pdf?sequence=1&isAllowed=y

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【 摘 要 】

Various methodologies were investigated to build synthetic intermediates from 1-acyl-2-dimethylphenylsilyl-2,3-dihydro-4-pyridones and to synthesize nicotine derivatives from nicotine.In the first part of this document, the synthesis and reactivity of 1-acyl-2-dimethylphenylsilyl-2,3-dihydro-4-pyridone were investigated.This dihydropyridone was synthesized from the addition of dimethylphenylsilyl Grignard to the 1-acyl-4-methoxypyridinium salt with a 90% yield and 98% de.A variety of reactions including 1,4-additions and the synthesis of the corresponding dihydropyridine was accomplished.In the second part, various methodologies were discovered to synthesize enantiopure nicotine derivatives from nicotine.Regioselective substitution reactions for functionalization at C-4, C-5 and C-6 of the pyridine ring were achieved.The synthesis of novel C-4 substituted and unsubstituted dihydronicotines was also developed.The von Braun reaction was applied to give enantiopure pyrrolidine ring-opened products.