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研究生:張國瑞
研究生(外文):Chang Kuo-Jui
論文名稱:鈀錯化合物催化1,2-雙烯之加成反應與應用及以鈷錯化合物為催化劑之偶合環化反應
論文名稱(外文):Palladium-Catalyzed Addition of Allenes and Its Application and Cobalt-Catalyzed Regioselective Carbocyclization
指導教授:鄭建鴻鄭建鴻引用關係
指導教授(外文):Cheng Chien-Hong
學位類別:博士
校院名稱:國立清華大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:中文
論文頁數:258
中文關鍵詞:Pd金屬錯合物有機碘化物矽硼試劑高位向選擇性及高立體選擇性羰基烯丙基化反應homoallylic alcohol 化合物鈷金屬錯化合物環化偶合反應indenol 之衍生物indene 之衍生物
外文關鍵詞:Palladium complexorganic iodideSilylboranhighly regio- and stereoselectivitycarboyl allytationhomoallylic alcoholCobalt complexcarbocyclizationindenolindene
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我們成功地使用Pd金屬錯合物與有機碘化物共同催化矽硼試劑加成到1,2-雙烯的反應;且此反應具有高位向選擇性及高立體選擇性,而且對於1,2-雙烯上的各種官能基有很好的容忍性。硼酯基是接於1,2雙烯的末端雙鍵上,而矽基是接於1,2雙烯中間碳上。而且就立體選擇性來說,主要的產物都是E form的形式。反應的反應機構是經由氧化加成I-Si鍵而啟動的,並不是直接的氧化加成Si-B鍵。此反應結果跟單純只用Pd金屬催化加成反應的結果是不一樣的。
我們並將此獨特之1,2-雙烯矽硼化反應用於homoallylic alcohol化合物之合成;單取代的1,2-雙烯(allene)、矽硼試劑(Silylboran)及醛類(aldehyde)可在鈀金屬、有機碘化物(organic iodides)共催化下於一鍋反應中得到新的homoallylic alcohol的產物,且產物有極高之極高之立體化學選擇性與立體化學異構性之保留(preservation of diastereospecificity),而且以syn form產物為主。尤其是具有芳香基取代基之1,2-雙烯(allene)化合物,syn form與anti form的選擇性大於99 / 1。而脂肪族取代基的1,2-雙烯化合物進行此類羰基烯丙基化反應,syn form與anti form的選擇性介於95/5-93/7之間。
我們成功地使用鈷金屬錯化合物來催化鄰-碘苯酮、鄰-碘苯醛與炔類之環化偶合反應得到成產物indenols,此反應具有不錯的反應產率及位向選擇性。對於一些非對稱之炔類,此環化偶合反應展現出異常好之位向選擇性,且得到單一之位向異構物。本催化系統相較其鈀金屬或鎳金屬錯合物來催化此偶合環化反應時,有著反應時間短、更具催化效率、且低經濟成本之優點。接下來並推測鈷金屬錯合物催化此環化偶合反應之反應機構。
此鈷金屬催化系統成功地延伸到烯類,並有效地催化鄰-碘苯酮、鄰-碘苯醛與烯類之環化偶合反應得到indene之衍生物;且此反應具有絕佳之位向選擇性及不錯的反應產率。此環化偶合反應所得之醇類產物會進一步進行脫水反應得到indene之產物,或者再進一步進行decyanation反應得到indene產物。
A highly regio and stereoselective method for the synthesis of various 2-silylallylboronates from allenes and silaborane catalyzed by palladium complexes and initiated by organic iodides is described. A variety of monosubstituted aryl and alkylallenes RCH=C=CH2 and 1,1-dimethylallene react with silaborane in the presence of Pd(dba)2 (5 mol %) and an organic iodide 3 (2-methyl-3-iodo-2-cyclohexen-1-one) (10 mol%) in EA at 80 oC to give the corresponding silaboration products in moderate to excellent yields. The product formation can be explained based on an unusual and new mechanistic pathway involving a three-component assembling reaction. This catalytic silaboration is totally regioselective with the silyl group of silaborane adding to the central carbon and the boryl group to the unsubstituted terminal carbon of allene. Furthermore, the reactions show very high stereoselectivity giving the corresponding E isomer as the major species.
And this silaboration chemistry can be applied to the synthesis of homoallylic alcohols. Treatment of allenes with silaborane and aldehydes in the presence of Pd(dba)2 (5 mol%) and alkenyl iodide 3 (10 mol%) at 80 °C in ethyl acetate for 5 h afforded homoallylic acohols in good yields with excellent syn selectivity.
An efficient cobalt-catalyzed carbocylization for the synthesis of indenols is described. 2-Iodophenylketones and 2-iodophenylaldehydes undergo carbocyclization with various disubstituted alkynes in the presence of CoI2(dppe), and zinc powder in acetonitrile at 80 oC for 3 h to afford the corresponding indenol derivatives in good to excellent yields. For some unsymmetrical alkynes, the carbocyclization was remarkably regioselective affording a single regioisomer. A possible mechanism for this cobalt-catalyzed carbocyclization reaction is proposed.
The cobalt-catalyzed carbocyclization reaction is successfully extended to the synthesis of indenes and a new method for reductive decyanation. Thus, the reaction of 2-iodophenylketones and 2-iodophenylaldehydes with acrylates H2C=CHCO2R proceeds smoothly in the presence of CoCl2(dppe) /dppe, and zinc powder in acetonitrile at 80 oC for 24 h to afford the corresponding indenes in moderate to good yields. Interestingly, when acrylonitrile H2C=CHCN was employed for the carbocylization, reductive decyanation also occurred to give indene derivatives without the cyano functionality. A possible mechanism for this cobalt-catalyzed carbocyclization reaction is also proposed.
第一章
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第三章
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第四章
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第五章
1. (a) Cahiez, G.; Avedissian, H. Tetrahedron Lett. 1998, 39, 6159. (b) Avedissian, H. Berillon, L.; Cahiez, G.; Knochel, P. Tetrahedron Lett. 1998, 39, 6163. (c) Ikeda, Y.; Nakamura, T.; Yorimtsu, H.; Oshima, K. J. Am. Chem. Soc. 2002, 124, 6514. (d) Fillon, H.; Gosmini, C.; Perichon, J. J. Am. Chem. Soc. 2003, 125, 3867. (e) Gomes, P.; Gosmini, C.; Perichon, J. Org. Lett. 2003, 5, 1043.
2. Matsuda, K.; Toyoda, H.; Kakutani, Koji; H., Masayuki; Ouchi, S.; ABCHA6; Agric.Biol.Chem.; EN; 54; 11; 1990; 3039-3040. (b) Boehme, T. M.; Keim, C.; Kreutzmann, K.; Linder, M.; Dingermann, T.; Dannhardt, G.; Mutschler, E.; Lambrecht, G.; JMCMAR; J.Med.Chem.; EN; 46; 5; 2003; 856 - 867. (c) Malleron, J.; Gueremy, C.; Mignani, S.; Peyronel, J.; Truchon, A.; et al.; JMCMAR; J.Med.Chem.; EN; 36; 9; 1993; 1194-1202.
3. (a) Gomes, P.; Gosmini, C.; Nedelec, J. -Y.; Perichon, J. Tetrahedron Lett. 2000, 41, 3385. (b) In another electrolysis method using nickel, indene was obtained as by-product; Condon, S.; Dupre, D.; Falgayrac, G.; Nedelec, J. –Y. Eur. J. Org. Chem. 2002, 105.
4. For recent reports on reductive decyanation, please see; (a) Vilsmaier, E.; Milch, G.; Bergstrasser, U. Tetrahedron 1998, 54, 6403. (b) Liu, H. J.; Yip, J. Synlett. 2000, 1119. (c) Walker, J. A.; Zhao, M.; Baker, M. D.; Dormer, P. G.; McNamara, J. Tetrahedron Lett. 2002, 43, 6747. (d) Guijarro, D.; Yus, M. Tetrahedron 1994, 50, 3447. (e) Kang, H. Y.; .Hong, W. S.; Cho, Y. S.; Koh, H. Y. Tetrahedron Lett. 1995, 36, 7661. (f) Curran, D. P.; Seong, C. M. J. Am. Chem. Soc. 1990, 112, 9401. (g) Curran, D. P.; Seong, C. M. Synlett 1991, 107.
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