臺灣博碩士論文加值系統

本篇論文報導新掌性N-乙醯腙的合成暨其非鏡像選擇性丙烯基三丁基錫的加成反應。掌性腙58a-58k可由便宜且直接購得的樟腦經過八個步驟來合成，總產率為18-26%。合成前驅物N-亞硝基氨基甲酸56可由氧化樟腦、還原空間障礙較小的羰基、形成N-苯甲基亞胺、立體選擇性還原亞胺、氫化苯甲基、胺醇的合環以及N-亞硝基化反應而得，總產率為35%。將亞硝基還原之後，接著與醛類縮合便可合成出雙鍵為E-型式的掌性腙58，並有中等的產率 (48-70%)。選用碘化鋅作為路易士酸是因為可使丙烯基加成反應完全以及方便操作等特性。丙烯基加成至由碘化鋅活化後的掌性腙後，可得到大部份由si-face加成的聯胺產物64，並在室溫下有極佳的產率 (98%) 和非鏡像超越值 (de > 98%)。

Synthesis and diastereoselective allyltributylstannane addition of novel chiral N-acyl hydrazones were described in this thesis. Hydrazones 58a-58k have been prepared from inexpensive commercially available (1R)-(+)-camphor in 18-26% yields over 8 steps. The synthetic precursor N-nitroso carbamate 56 was synthesized from camphor through oxidation, selective reduction of less hindered carbonyl group, N-benzyl imine formation, stereoselective reduction of imine, hydrogenation of benzyl group, cyalization of aminoalcohol and N-nitrosylation in an 35% overall yield. Reduction of nitroso group followed by condensation with aldehydes afforded E-form hydrazones 58 in moderate isolated yields (48-70%). ZnI2 was chosen as Lewis acid base on full conversion of the allylation and ease to handle. Allylation of ZnI2 activated hydrazone gave mostly si-face addition and furnished homoallylic hydrazine 64 in excellent yield (98%) and diastereomeric excess (de > 98%) under room temperature.

中文摘要 iv
英文摘要 v
壹、前言 1
貳、結果與討論
1. Synthesis of novel N-acyl hydrazones derived from (+)-camphor 22
2. Diastereoselective allylation to N-acyl hydrazones in the presence of
ZnI2 as Lewis acid 30
3. Representative methods for N-N bond cleavage reaction 34
4. Conclusion 41
參、儀器測定部份及溶劑 42
肆、實驗步驟 43
伍、參考文獻 75
陸、化合物1H與13C核磁共振光譜 80

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