臺灣博碩士論文加值系統

摘 要
以鈀金屬錯合物Pd(dba)2為催化劑可以成功的使苯基或烯基碘化物、1,2雙稀，及有機雙錫試劑在一鍋反應之下，進行三體偶合反應（three components coupling），成功的得到在b及g位置具有取代基的丙烯基有機錫試劑。此加成反應都是發生在1,2雙烯末端未取代的雙鍵上，具有很高的位向選擇性。使用單取代的1,2雙烯，反應會有立體選擇性，產物以Z form較多，E form較少。
醯氯化物(acyl chloride)與1,2-雙烯(allene)及雙硼試劑(diboran)，在零價或貳價的無PPh3配位基的鈀金屬錯合物催化之下，可以進行三分子偶合反應(three component coupling reaction)，得到高取代基的丙烯基硼試劑。在中性的反應條件底下反應就可以進行，不需要額外加鹼。而且反應過程中，醯氯化物的CO group，完全被保留下來。此反應不僅具有極佳的E form立體選擇性以及位向選擇性（在1,2-雙烯末端雙鍵上做加成反應），而且對於醯氯化物上的各種官能基有很好的容忍性。
雙硼試劑加成到1,2雙烯的反應，傳統上利用Pt金屬錯合物為催化劑，根據文獻的報導，單獨只使用Pd金屬錯合物是無法進行此反應的。但我們發現可以使用Pd金屬錯合物與有機碘化物共同催化下的系統，來進行此種加成反應。溶劑的選擇以甲苯為最佳，Pd錯合物以沒有強配位基存在為最好的選擇。反應具有高位向選擇性及高立體選擇性。兩個硼酯基都接於丙二烯基沒有取代的末端雙鍵上。立體選擇性很高，主要的產物都是Z form的形式。利用我們的實驗方法，可以合成出特殊的含有芳香族碘化物取代的雙硼酯基烯類產物。而這類化合物，利用傳統的催化方法（使用Pt金屬錯合物）是無法達到的。此加成反應的反應機構是經由I-B鍵氧化加成而啟動的，並不是直接B-B鍵的氧化加成。
有機碘化物（organic iodides）或是有機溴化物（organic bromides）與1,2-雙烯(allene)及雙硼試劑(diboran)，在零價或貳價的無PPh3配位基的鈀金屬錯合物催化之下，以及鹼性條件下，也可以進行三分子偶合反應(three component coupling reaction)，得到高取代基的丙烯基硼試劑。反應加鹼，可以成功的避免雙硼試劑加成到1,2雙烯上。所使用的鹼類可以是有機鹼或無機鹼。為了考慮溶解度的問題，必須使用高極性的溶劑。若是溶解度不佳，反應會出現雙硼化反應的產物。

Abstract:
Aryl or alkenyl iodides react regioselectively with allenes and hexaalkylditins in the presence of Pd(dba)2 to give substituted allylstannanes.
A highly regio- and stereoselective method for the synthesis of 2-acylallylboronates based on a palladium-catalyzed three-component assembling of acyl chlorides, allenes and bis(pinacolato)diboron is described. Treatment of CR2R3=C=CH2 (R2 = R3 = Me; R2 = H, R3 = n-Bu; R3 = Ph; R3 = cyclohexyl; R3 = t-Bu) with acyl chlorides (R1COCl: R1 = p-MeOC6H4, p-NO2C6H4, C6H5, p-MeO2CC6H4, 1-naphthyl, 2-thienyl, 5-isooxazolyl, t-BuCH2, i-Bu, and Bn) and 3 in the presence of Pd(MeCN)2Cl2 in toluene at 80 °C gave 2-acylallylboronates in good to excellent yields. The acyl group adds to the allene without decarbonylation. In addition, no extra base is required to activate diboron in the reaction. These addition reactions are completely regioselective and for mono substituted allenes, the reactions also show extremely high E stereoselectivity. A mechanism based on a face-selective coordination of allenes to the palladium center is proposed to account for the present stereoselectivity.
A highly regio- and stereoselective diboration of allenes was achieved with a catalytic amount of phosphine-free Pd complex and alkenyl or aryl iodide. Thus. Treatment of CR1R2=C=CH2 (R1 = R2 = Me; R1 = H, R2 = n-Bu; R2 = Ph; R2 = cyclohexyl; R2 = cyclopentyl, R2 = C6H5O, R2 = 2-IC6H4O, R2 = 4-IC6H4O) with bis(pinacolato)diborn in the presence of Pd(dba)2 (5 mol %) and 3-iodo-2-methyl-2-cyclohexen-1-one (5 mol %) in toluene at 80 oC gave products bearing both vinylic and allylic boron moieties in good to excellent yields. No diboration occurs in the absence of either a Pd complex or alkenyl iodide. In all cases, only the biboronic products with one boryl group adding to the middle carbon and the other to the nonsubstituted terminal carbon of the allene moiety were observed. This Pd-catalyzed reaction proceeds via a previously unknown mechanism involving the oxidative addition of an I-B bond to the palladium center instead of the oxidative addition of a B-B bond to metal. The substituent on the allene group shows little effect on the yield of biboronic product. A face-selective coordination of allene to the palladium center is proposed to account for the present stereoselectivity.
A highly regioselective method for the synthesis of allylboronates based on a palladium-catalyzed three-component assembling of organic halides, allenes and bis(pinacolato)diboron is described. Treatment of dimethyl allene with organic iodides or bromides and diboron in the presence of Pd(dba)2 in DMF at 60 °C in the presence of excess base such as KOAc or K2CO3 gave allylboronates in good to excellent yields. These addition reactions are completely regioselective. In all cases, only the product which the organic group adding to the middle carbon and the boryl group to the nonsubstituted terminal carbon of the allene moiety were observed. These allylboronates show good reactivity to benzaldehyde to give homo allylic alcohols.
中文摘要 ----------------------------------------------------------------------------- i
英文摘要 ----------------------------------------------------------------------------- iii
圖目錄 ----------------------------------------------------------------------------- v
第一章 緒論 -------------------------------------------------------------- 1
參考文獻 ------------------------------------------------------------- 28
第二章 鈀金屬錯合物催化1,2-雙烯與有機鹵化物及有機雙錫試劑的偶合反應---多取代丙烯基錫試劑的合成
前言 ------------------------------------------- 35
結果與討論 ------------------------------------------- 41
結論 ------------------------------------------- 58
實驗部分及光譜資料 ------------------------------------------- 59
參考文獻 ------------------------------------------- 79
附錄1H-NMR光譜圖 ------------------------------------------- 83
第三章 鈀金屬錯合物催化1,2-雙烯與有機醯氯化物及有機雙硼試劑的偶合反應---醯基丙烯基硼試劑的合成
前言 ------------------------------------------- 107
結果與討論 ------------------------------------------- 111
結論 ------------------------------------------- 129
實驗部分及光譜資料 ------------------------------------------- 131
參考文獻 ------------------------------------------- 147
附錄1H-NMR光譜圖 ------------------------------------------- 149
第四章 鈀金屬錯合物催化有機雙硼試劑加成到1,2-雙烯之雙硼化反應---丙烯基雙硼試劑的合成
前言 ------------------------------------------- 169
結果與討論 ------------------------------------------- 176
結論 ------------------------------------------- 206
實驗部分及光譜資料 ------------------------------------------- 207
參考文獻 ------------------------------------------- 227
附錄1H-NMR光譜圖 ------------------------------------------- 231
第五章 鈀金屬錯合物催化有機鹵化物與1,2-雙烯及有機雙硼試劑的偶合反應---多取代丙烯基硼試劑的合成
前言 ------------------------------------------- 241
結果與討論 ------------------------------------------- 241
結論 ------------------------------------------- 254
實驗部分及光譜資料 ------------------------------------------- 255
參考文獻 ------------------------------------------- 270
附錄1H-NMR光譜圖 ------------------------------------------- 271

封面
中文摘要
英文摘要
謝誌
圖目
第一章　緒論
參考文獻
第二章　鈀金屬錯合物催化１，２－雙烯與有機鹵化物及有機雙錫試劑的偶合反應－－多取化丙烯基鉍試劑的合成
前言
結果與討論
結論
實驗部分及光譜資料
參考文獻
附錄1H-NMR光譜圖
第三章　鈀金屬錯合物催化１，２－雙烯與有機醯氯化物及有機雙硼試劑的偶合反應－醯基丙烯基硼試劑的合成
前言
結果與討論
結論
實驗部分及光譜資料
參考文獻
附錄1H-NMR光譜圖
第四章　鈀金屬錯合物催化有機雙硼試劑加成到１，２－雙烯之雙硼化反應－－丙烯基雙硼試劑的合成
前言
結果與討論
結論
實驗部分及光譜資料
參考文獻
附錄1H-NMR光譜圖
第五章　鈀金屬錯合物催化有機鹵化物與１，２－雙烯及有機雙硼試劑的偶合反應－－取化丙烯基硼試劑的合成
前言
結果與討論
結論
實驗部分及光譜資料
參考文獻
附錄1H-NMR光譜圖
化合物5c的1HNMR光譜

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