CuI催化氨基酸促进的Ullmann类碳—碳键交叉偶联反应研究
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摘要
过渡金属催化的交叉偶联反应可以方便地生成sp~2碳-碳、碳-杂键,是有机合成的重要手段之一。与钯、镍等过渡金属相比,铜是一种廉价而且低毒的金属,用铜来催化这些交叉偶联反应不仅可以节省贵金属的消耗以降低成本,而且可以减少对环境的污染、促进绿色化学的发展。不对称碳-碳键的合成反应,尤其是手性季碳中心的构建反应,是有机合成研究的一个重点和难点所在,对于有机合成的应用和发展具有重要意义。本文的主要工作就是氨基酸促进的铜催化的芳基卤化物与活泼亚甲基化合物的交叉偶联反应以及不对称的2-取代-β-酮酯的α-芳基化反应研究。
在本文的第二章中,我们研究了铜催化氨基酸促进的芳基卤化物与活泼亚甲基化合物的交叉偶联反应。以4-碘茴香醚与乙酰乙酸乙酯为模板反应,我们考察了不同反应条件对反应结果的影响,最后筛选出了最佳反应条件:0.2 eq CuI、0.4eq L-proline、4eq Cs_2CO_3、DMSO、40℃。以此标准条件,我们对以不同结构的芳基碘化物作为底物和不同的活泼亚甲基化合物的反应进行了考察,并发现大部分的芳基碘化物都可以与乙酰乙酸乙酯、丙二酸二乙酯或苯甲酰乙酸乙酯发生偶联反应得到良好收率的偶联产物。芳环吸电子基取代的芳基碘化物表现出更高的反应活性。我们还研究了芳基溴化物与活泼亚甲基化合物的偶联反应,并发现在相似的反应条件下,大部分的芳基溴化物都可以与乙酰乙酸乙酯、丙二酸二乙酯或苯甲酰乙酸乙酯发生偶联反应得到中等至良好收率的偶联产物。我们对反应的机理进行了推测,并认为反应是按照氧化加成/还原消除的机理进行的。
在第三章中,我们研究了铜催化氨基酸促进的2-取代-β-酮酯的不对称α-芳基化反应。我们对不同底物、反应物、溶剂、配体和碱对反应的影响进行了研究,通过研究我们发现,在配体、邻基效应和溶剂的共同作用下,反应可以很好的进行,当以邻碘三氟乙酰苯胺衍生物为底物、2-甲基乙酰乙酸叔丁酯为反应物、CuI为催化剂、L-羟基脯氨酸为配体、NaOH为碱、DMF为溶剂、添加适量水时,反应在-45℃即可进行,并且当芳环上带有推电子基取代时,反应给出了最好的立体选择性,最高达到93%ee,而芳环上带有吸电子基取代的底物,在一定条件下也可反应,并给出较好结果。通过将一个反应产物转化为已知的氧化吲哚类化合物,我们确定了产物的绝对构型为S。对于芳基溴化物以及其它的一些β-酮酯化合物,在相似的条件下反应也可进行,但不对称选择性相对较差。我们也对反应的机理进行了一些研究,初步认为反应是按照氧化加成/还原消除的机理进行的,并对实验中的一些特殊现象进行了解释。
The transition metal-catalyzed cross-coupling reactions to form sp~2 C-C or C-hetero atom bonds have received considerable attention in the past decades.In comparison with Pd and Ni,copper is a cheaper metal with lower toxicity.Asymmetric carbon-carbon bond cross-coupling reactions,especially the construction of all-carbon quaternary stereo center, are an important part of organic synthesis and still full of challenge.In this dissertation we wish to report our recent investigations on the cross-coupling reactions of aryl halides with activated methylene compounds under the catalysis of CuI and amino acids,and the asymmetricα-arylation reaction of 2-substitutedβ-keto esters.
In the chapter 2 of this dissertation,we reported the cross-coupling reaction of aryl halides with activated methylene compounds under the catalysis of CuI and amino acid. Using the coupling of 4-iodoanisole with ethyl acetoacetate as a model reaction,we explored the optimized conditions.These conditions were then tested by using several electron-rich or electron-deficient aryl iodides,β-keto esters and diethyl malonates.It was found that most of them were successfully converted to the corresponding products in good to excellent yields.Further studies indicated that aryl bromides under the similar reaction conditions gave moderate to good yields of coupling products.Electron-rich aryl iodides or bromides showed higher reactivities in comparison with electron-deficient ones.We proposed that this reaction might go through the oxidative addition/reductive elimination mechanism.
In the chapter 3 of this dissertation,we studied the asymmetricα-arylation reaction of 2-substitutedβ-keto esters under the catalysis of CuI and amino acid.After screening substrates,reactants,solvents,ligands and bases,we found that when 2-iodotrifluoroacetanilides were used as the substrates,t-butyl 2-methylacetoacetates as a coupling partner,CuI as the catalyst,L-4-hydroxyproline as the ligand,NaOH as a base, DMF as the solvent and small amount of water as additive,the reactions can be carried out at -45℃to give the corresponding coupling products in good yields and good to excellent enatioselectivity.By converting a coupling product into a known oxindole compound in two steps,we concluded that the absolute configuration of our coupling products is S.We also proposed that this reaction might go through the oxidative addition/reductive elimination mechanism.
在本文的第二章中,我们研究了铜催化氨基酸促进的芳基卤化物与活泼亚甲基化合物的交叉偶联反应。以4-碘茴香醚与乙酰乙酸乙酯为模板反应,我们考察了不同反应条件对反应结果的影响,最后筛选出了最佳反应条件:0.2 eq CuI、0.4eq L-proline、4eq Cs_2CO_3、DMSO、40℃。以此标准条件,我们对以不同结构的芳基碘化物作为底物和不同的活泼亚甲基化合物的反应进行了考察,并发现大部分的芳基碘化物都可以与乙酰乙酸乙酯、丙二酸二乙酯或苯甲酰乙酸乙酯发生偶联反应得到良好收率的偶联产物。芳环吸电子基取代的芳基碘化物表现出更高的反应活性。我们还研究了芳基溴化物与活泼亚甲基化合物的偶联反应,并发现在相似的反应条件下,大部分的芳基溴化物都可以与乙酰乙酸乙酯、丙二酸二乙酯或苯甲酰乙酸乙酯发生偶联反应得到中等至良好收率的偶联产物。我们对反应的机理进行了推测,并认为反应是按照氧化加成/还原消除的机理进行的。
在第三章中,我们研究了铜催化氨基酸促进的2-取代-β-酮酯的不对称α-芳基化反应。我们对不同底物、反应物、溶剂、配体和碱对反应的影响进行了研究,通过研究我们发现,在配体、邻基效应和溶剂的共同作用下,反应可以很好的进行,当以邻碘三氟乙酰苯胺衍生物为底物、2-甲基乙酰乙酸叔丁酯为反应物、CuI为催化剂、L-羟基脯氨酸为配体、NaOH为碱、DMF为溶剂、添加适量水时,反应在-45℃即可进行,并且当芳环上带有推电子基取代时,反应给出了最好的立体选择性,最高达到93%ee,而芳环上带有吸电子基取代的底物,在一定条件下也可反应,并给出较好结果。通过将一个反应产物转化为已知的氧化吲哚类化合物,我们确定了产物的绝对构型为S。对于芳基溴化物以及其它的一些β-酮酯化合物,在相似的条件下反应也可进行,但不对称选择性相对较差。我们也对反应的机理进行了一些研究,初步认为反应是按照氧化加成/还原消除的机理进行的,并对实验中的一些特殊现象进行了解释。
The transition metal-catalyzed cross-coupling reactions to form sp~2 C-C or C-hetero atom bonds have received considerable attention in the past decades.In comparison with Pd and Ni,copper is a cheaper metal with lower toxicity.Asymmetric carbon-carbon bond cross-coupling reactions,especially the construction of all-carbon quaternary stereo center, are an important part of organic synthesis and still full of challenge.In this dissertation we wish to report our recent investigations on the cross-coupling reactions of aryl halides with activated methylene compounds under the catalysis of CuI and amino acids,and the asymmetricα-arylation reaction of 2-substitutedβ-keto esters.
In the chapter 2 of this dissertation,we reported the cross-coupling reaction of aryl halides with activated methylene compounds under the catalysis of CuI and amino acid. Using the coupling of 4-iodoanisole with ethyl acetoacetate as a model reaction,we explored the optimized conditions.These conditions were then tested by using several electron-rich or electron-deficient aryl iodides,β-keto esters and diethyl malonates.It was found that most of them were successfully converted to the corresponding products in good to excellent yields.Further studies indicated that aryl bromides under the similar reaction conditions gave moderate to good yields of coupling products.Electron-rich aryl iodides or bromides showed higher reactivities in comparison with electron-deficient ones.We proposed that this reaction might go through the oxidative addition/reductive elimination mechanism.
In the chapter 3 of this dissertation,we studied the asymmetricα-arylation reaction of 2-substitutedβ-keto esters under the catalysis of CuI and amino acid.After screening substrates,reactants,solvents,ligands and bases,we found that when 2-iodotrifluoroacetanilides were used as the substrates,t-butyl 2-methylacetoacetates as a coupling partner,CuI as the catalyst,L-4-hydroxyproline as the ligand,NaOH as a base, DMF as the solvent and small amount of water as additive,the reactions can be carried out at -45℃to give the corresponding coupling products in good yields and good to excellent enatioselectivity.By converting a coupling product into a known oxindole compound in two steps,we concluded that the absolute configuration of our coupling products is S.We also proposed that this reaction might go through the oxidative addition/reductive elimination mechanism.
引文
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