一、 經由兩次 Michael 及縮醛化連續性反應合成出具有高化學及立體選擇性之雙環橋形 [3.3.1] 九員環骨架化合物 二、 製備新穎的 Wittig 試劑以合成多官能基取代的烯類化合物
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2015
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本論文主要研究分為兩大部分：
第一部份：α,β-不飽和雙酮化合物 79 作為親核性試劑，與 1,3-茚二酮反應，以 Michael-Michael-acetalization 反應建構雙環橋形 [3.3.1] 九員環骨架化合物。
第二部分：製備新穎的 Wittig 試劑以合成多官能基取代的烯類化合物
第一部分，經由 α,β-不飽和雙酮化合物 79 和 1,3-茚二酮的有機不對稱反應，建構具有四級碳的多取代雙環橋形 [3.3.1] 九員環骨架化合物 81 ，此反應的單一鏡像異構物，產率為 10-84%，鏡像超越值可高達 85%。
(產物尚未解出絕對立體組態，先以相對立體結構表示)
第二部分，利用活性烯類與三丁基膦合成新穎的 Wittig 試劑後，與 Michael 受質 131 及醛類分子 132 反應，經由高立體選擇性之 Wittig 反應合成出具有多取代烯類產物 133，產率為 43-92%。
This thesis is divided into two parts： Part 1. Synthesis of bicyclo[3.3.1]nonane derivatives via organocatalytic asymmetric double Michaal-acetalization reaction with α,β-unsaturated 1,3-diketones and 1,3-indandiones Part 2. Synthesis of multi-functional alkenes via Wittig Reaction with a new-type of phosphorus ylide In the first part, a series of novel bicyclo[3.3.1]nonane derivatives with a quaternary stereocenter were synthesized via organocatalytic asymmetric double Michael-acetalization reaction of α,β-unsaturated 1,3-diketones 79 and 1,3-indandiones 80. In the second part, we have developed a new type of Wittig reagent from PBu3 and Michael acceptors 131, which could be utilized in the Wittig reaction with a variety of aldehydes 132 to synthesize multi-functional alkenes 133 with excellent stereo-selectivity.
This thesis is divided into two parts： Part 1. Synthesis of bicyclo[3.3.1]nonane derivatives via organocatalytic asymmetric double Michaal-acetalization reaction with α,β-unsaturated 1,3-diketones and 1,3-indandiones Part 2. Synthesis of multi-functional alkenes via Wittig Reaction with a new-type of phosphorus ylide In the first part, a series of novel bicyclo[3.3.1]nonane derivatives with a quaternary stereocenter were synthesized via organocatalytic asymmetric double Michael-acetalization reaction of α,β-unsaturated 1,3-diketones 79 and 1,3-indandiones 80. In the second part, we have developed a new type of Wittig reagent from PBu3 and Michael acceptors 131, which could be utilized in the Wittig reaction with a variety of aldehydes 132 to synthesize multi-functional alkenes 133 with excellent stereo-selectivity.
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有機不對稱反應, 多官能基烯類化合物, Wittig 反應, Organocatalysis, multi-functional alkenes, Wittig reaction