臺灣博碩士論文加值系統

過去二十幾年來的文獻顯示，α-蒎烯(α-pinene)的衍生物的兩個純掌性異構物，包括(+)和(-)的2-Hydroxypinan-3-one 及(+)-和(-)-3-Amino-2-
Hydroxypinane，已可經由幾個簡單的步驟而獲得，是一個相當不錯的掌性來源。最近，具有具高純度之鏡像胺基醇，例如：(+)- and (-)-3-Amino-2- Hydroxypinane, 已在論文上被報導出來。然而，在合成高純度之N-取代胺基醇，除了1989年Karolak-Wojciechowska 所合成之胺基醇, 已有其餘之N-取代胺基醇可經由合成製備而得。
為了要改善1989年J. Karolak-Wojciechowska所合成之一系列的N-取代胺基醇，我們利用一個明確的方法去製備只有同向之N-取代胺基醇。我們以cis-3-Amino-2- hydroxypinane為起始物與一些不同取代基的酮類做加成反應形成imino之中間產物再以LiAlH4還原。在合成出一系列的N-取代胺基醇後，將磷配位基帶入此胺基醇，形成一個具磷的掌性催化劑。再將其應用在Hydrazone的磷酸化反應中，使之形成一個具掌性的α-hydrazino-
phosphonates。
而純的N-取代胺基醇也是非常有用的掌性輔助基，可用於不對稱合成中並用來用來製備許多不同的掌性物質。

For the last two decades it has shown that α-pinene is a good source for the synthesis of various chiral materials which resulted in the commerciallizations of, for example, (+)- and (-)-2-Hydroxypinan-3-one. Recently, enantiomerically pure amino alchohols, such as (+)- and (-)-3-Amino-2- Hydroxypinane, have also been reported. However, little has been mentioned for the synthesis of enantiomerically pure N-substituted aminoalcohols, except the works done by Karolak-Wojciechowska in 1989, in which whether the N-substituted amino alcohols have been prepared with high stereoselectivity is questionable.
In order to examine the stereoselectivity of a series of N-substituted amino alcohols synthesized by J. Karolak-Wojciechowska’s group , we have used an unambiguous method to prepare only cis form of N-substituted amino alcohols. We use pure cis-3-Amino-2-hydroxypinane as a starting material which was condensed with several different ketones and the resulted imono intermediates were then reduced with LiAlH4. The pure N-substituted amino alcohols have been converted to form a new phosphorus-containing chiral auxiliary, namely chiral cyclic phosphonate. We are currently using this new chiral phosphonate to do the phosphonylation of hydrazones in order to prepare novel chiral α-hydrazinophosphonates.
The pure N-substituted amino alcohols are also useful as chiral auxiliaries for the asymmetric synthesis in the preparation of a variety of chiral materials.

目錄：
中文摘要.............................................. I
英文摘要............................................. II
誌謝................................................ III
目 錄................................................ IV
圖 目 錄............................................. VI
表 目 錄 .......................................... VIII
反應流程目錄 ........................................ IX

壹、緒論
緒 論 ............................................ 01
1-1 前言…………………………………………………… 01
1-2 以樟腦為骨架的立體修飾劑………………………… 03
1-3以蒎烯為骨架的立體修飾劑…………………………… 06
1-4 本論文之研究目標…………………………………… 12
1-4-1 親核加成與磷酸化反應(Pudovic reaction)………14
1-4-2 磷酸化反應之文獻………………………………… 18

貳、 逆合成與合成路徑……………………………….. 23
2-1合成路徑A…………………………………………………25
2-2合成路徑B (文獻方法)………………………………… 26
2-3合成路徑C (新路徑)…………………………………… 27

參、實驗結果與討論…………………………………………28

肆、實驗藥品與測試儀器……………………………………38

伍、實驗步驟與數據…………………………………………39

陸、參考文獻…………………………………………………123

附錄 1H 光譜與13C 光譜............................126

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