高活性烯類在製備新穎的Wittig試劑之合成與應用以及有機催化反應上的研究

Abstract

本論文係主要利用具有強烈拉電子官能基的活潑烯類分子I分別進行有機合成。首先當R1為苯甲醯基時，烯類分子I在醯氯化合物與三丁基膦反應下可形成Wittig試劑，接著在三乙基胺反應下，可生成多官能基取代的呋喃化合物II；當R為乙酯基以及R1為氫原子時，在三丁基膦反應下亦可形成另一種Wittig試劑，接著與醛類化合物進行反應，可生成多官能基取代烯類分子III；而當R與R1同為氫原子時，分別在二苯基乙基膦催化下，與醛類分子以及親核性試劑反應，或在三苯基膦催化下，與亞胺分子以及親核性試劑反應，可生成多官能基取代的三組分產物IV；最後在二級胺催化劑催化下與環己酮進行有機不對稱加成反應，可生成多官能基取代的不對稱產物V。Activated alkenes (I) containing electron-withdrawing group are used for the synthetic organic transformations in this thesis. At first, when R1 is benzoyl group, in situ formed phosphonium salts resulted from I, tributylphosphine, and acyl chlorides are deprotonated by triethylamine to provide multisubstituted furans II. When R is CO2Et and R1 is hydrogen, alkenes I react with tributylphosphine and various aldehydes to afford highly functionalized alkenes III. When R and R1 are hydrogen, the reactions of alkenes I, aldehydes or imines, and the corresponding nucleophiles catalyzed by ethyl diphenylphosphine or triphenylphosphine proceed successfully to furnish the multi-functional adducts IV. Finally, alkenes I can also undergo asymmetric, organocatalytic Michael additions with cyclohexanone catalyzed by chiral secondary amine to yield the highly functional products V with high stereoselectivities.