臺灣博碩士論文加值系統

本篇論文主要-胺基酸 (-amino acid) 不對稱合成上所需的光學輔助基的製備方法。我們以三個合成步驟成功地製備出總產率60%的光學輔助基化合物17，以及以五個合成步驟製備出總產率55%的光學輔助基化合物35。其中我們利用Sharpless二羥基化反應 (dihydroxylation) 建立光學輔助基的立體化學 (stereo chemistry)，所得化合物16, 32的光學純度分別是94%, 96% (enantiomeric excess, e.e.)，在後續製備光學輔助基的反應步驟中並未發現有光學純度降低的現象。
另外，我們發現位於掌性模板 (chiral template) 化合物20 C-6位置上的氫，在強鹼的條件下會進行去質子化反應 (deprotonation) 而得到非我們預期的產物27，其結構已由X-ray單晶繞射確定。因此我們製備出另一個在C-6位置上的氫以甲基取代的掌性模板化合物37，不論以強鹼二異丙胺化鋰 (lithium diisopropylamide, LDA) 的條件或是以碳酸鉀當鹼在相轉移催化 (phase-transfer catalyst, PTC) 的條件下進行芐基化以及丙烯基化，皆可獲得化合物38產率為68~75%，光學選擇性 (diastereoselectivities) 為>98%的結果。

This thesis describes our studies on the asymmetric synthesis of alpha-amino acids utilizing monocyclic iminolactones as chiral templates. Chiral auxiliaries 17 and 35 were prepare in three and five steps with the overall yield of 60 % and 53 % respectively. The stereocenter was established by employing Sharpless asymmetric dihydroxylation to furnish compounds 16 and 32 with 94 % and 96 % entiantiomeric excess (e.e.) respectively. No recemization of compounds 17, 35 during the transformations was observed.
When alkylation of chiral template 20 was carried out using LDA as the base, deprotonation at C-6 occurred leading to the formation of unwanted product 27. Consequently, the structure of 27 was confirmed by single X-ray crystal analysis. Use of chiral template, 37 having methyl group in place of C-6 hydrogen, has been prepared. Benzylation or allylation with benzyl or allyl bromide using different bases, such as LDA or potassium carbonate and a phase-transfer catalyst (PTC), resulted in the formation of the alkylated product 38 with 68-75% yield and >98% diastereoselectivity.

中文摘要 v
英文摘要 vi
壹、緒論 1
一、-胺基酸的重要性 1
二、-胺基酸的逆合成分析 3
三、胺基酸不對稱合成範例 4
貳、結果與討論 22
一、掌性模板製備：策略一 22
二、掌性模板製備：策略二 31
三、掌性模板製備：策略三 39
四、結論 44
參、儀器測定及溶劑 45
肆、實驗步驟與化合物光譜 47
伍、參考資料 69
陸、附錄 76

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