臺灣博碩士論文加值系統

一、手性醛醇縮合的應用
摘要：
在四氯化鈦輔助下，樟腦基架衍生的手性烯醇鹽，可經由一鍋反應的方式進行溴化及醛醇加成反應，不但產率高，選擇性更是好 (>99:1)，此一醛醇加成物在DMAP (4-dimethylaminopyridine) 的催化下，和加入的水、醇或胺進行脫醯反應，可分別轉換成α-溴-β-羥基酸、酯及醯胺類化合物，同時並可回收手性樟腦基架。由於α碳上的溴是相當好的離去基，所以不僅可與NaN3進行疊氮置換溴的反應，獲得α-疊氮基-β-羥基的酯類，亦可利用α碳上的羥基做一次分子內的SN2 反應取代α碳上的溴，並翻轉α碳上的立體化學，形成環氧酸或酯類。另外，α碳上的溴可利用鋁汞齊 (Al-Hg) 進行低溫 (0 ℃) 還原去溴，即使分子內有其它官能基 (如雙鍵、溴、氯…) ，仍可選擇性的將手性溴醇 (bromohydrins) 去溴，而不破壞其它官能基，不影響原有立體化學中心，得到純光學活性的α-無取代-β-羥基酸、酯或醯胺類。
二、探討生物鹼Pancratistatin的合成
摘要：
我們可利用源自同一手性源的樟腦醯亞硝和樟腦氯亞硝，與雙烯進行高選擇性的環化加成反應，建立兩種互為手性異構的氮氧雜環加成物。樟腦氯亞硝和O-isopropylidenedioxycyclohexadiene進行加成反應，所產生的手性不飽和胺醇 (4-amino-5,6-O-isopropylidenedioxy-
cyclohex-2-en-1-ol)，被用做研究合成具有生物活性的(+)-pancratistatin生物鹼。

Demonstration of the Synthetic Utility of Bromination-Aldolizations
of Camphor-Based Chiral N-Acetyloxazolidinethione
Abstract：
TiCl4-promoted one pot enolate bromination-aldolizations of amphor-
based chiral N-acetyloxazolidinethione are highly diastereoselective (>99:1) and high-yielding processes. DMAP-mediated deacylation of carboxthioimide adducts can be directed to form α-bromo-β-hydroxy acids, ester, and amides along with a recovery of the camphor-based chiral auxiliary. To expand the scope of this deacylation methodology to the α,β-epoxy ester formation, we have established the feasibility to redirect this reaction from a simple deacylation pathway to a deacylation-
substitution route. Treatment of the deacylation intermediates, generated in situ, with NaN3 led to smooth displacement of the bromide to give azide. The bromohydrin intermediates can also be converted to α,β-epoxy esters via internal SN2 substitution. On the other hand, the Al-Hg promoted chemoselective debromination allows for a clean transformation of bromohydrin aldols into β-hydroxy acid derivatives in the presence of highly sensitive functionality. This Al-Hg mediated reductive cleavage of C-Br bond provides a facile approach to optically pure β-hydroxy acids, esters, and amides with no detectable levels of epimerization.
Synthetic Studies of Pancratistatin Alkaloids
Abstract：
We have established the feasibility of employing the same chiral auxiliary to obtain different chiral nitroso synthons, acylnitroso and chloronitroso, for construction of both antipodes of bicyclic oxazines in high enantioselectivity through cycloaddition reactions. Enantiomerically pure 4-amino-5,6-O-isopropylidenedioxycyclohex-2-en-1-ol, conveniently prepared by the union of O-isopropylidenedioxy-
cyclohexadiene with camphor-based chiral chloronitroso, was employed in the study of synthesis of (+)-pancratistatin alkaloids which possess a wide spectrum of biological activities.

目錄
一、手性醛醇縮合的應用 (中文摘要)………………………………..1
一、手性醛醇縮合的應用 (英文摘要)………………………………..2
第一章 高選擇性的α-溴烯醇鹽的加成反應
緒論…………………………………………………………………3
結果與討論…………………………………………………………4
結論…………………………………………………………………6
第二章 利用脫醯反應將醛醇加成物轉換成α-溴-β-羥基酸、酯及醯
胺
緒論………………………………………………………………….7
結果與討論………………………………………………………….9
結論………………………………………………………………...12
第三章 合成手性α-疊氮基-β-羥基的酯類及手性反式-α,β-環氮酯
緒論………………………………………………………………13
結果與討論………………………………………………………16
結論………………………………………………………………18
第四章 合成純手性順式-α,β-環氧酸或酯
緒論………………………………………………………………19
結果與討論………………………………………………………20
結論………………………………………………………………..22
第五章 利用鋁汞合金將手性溴醇 (Bromohydrins) 化合物做選擇性
的去溴，轉化成純手性α-無取代-β-羥基化合物
緒論………………………………………………………………23
結果與討論………………………………………………………25
結論………………………………………………………………32
儀器測定部分及試劑…………………………………………………33
實驗步驟與光譜資料…………………………………………………34
參考文獻……………………………………………………………57
二、探討生物鹼Pancratistatin的合成 (中文摘要)……………………58
二、探討生物鹼Pancratistatin的合成 (英文摘要)……………………59
第一章 樟腦基架亞硝和各種醯類進行不對稱 hetero Diels-Alder反應
之探討
緒論………………………………………………………………...60
結果與討論………………………………………………………...62
結論………………………………………………………………...71
第二章 生物鹼Pancratistatin的合成研究
緒論………………………………………………………………...72
結果與討論………………………………………………………...77
結論…………………………………………………………….…. 95
儀器測定部分及試劑…………………………………………………..96
實驗步驟與光譜資料………………………………………………..…97
參考文獻………………………………………………………………148
X-ray 光譜圖………………………………………………………….151
NMR光譜圖…………………………………………………………...156
發表期刊 (publications) ……………………………………………...475

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