铁催化构建C-N和C-O键的研究
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摘要
很多天然产物、药物和染料都大量的C-N、C-O键,因而采用金属催化有机反应来构建C-N、C-O键是一种有效的策略。铁盐和铜盐具有价格便宜、低毒等优点,因而能够用于有机反应催化中。本论文将铁催化剂和铁/铜共催化剂,用于Ullmann N-和O-芳基化、烯烃氨卤化和C-H键酰胺化三类反应中,取得了如下重要研究成果:
建立了一种高效、廉价的双金属催化剂FeCl_3/CuO/消旋化的BINOL,可以极大的催化脂肪胺、芳基胺和酚的N、O-芳基化,而且在交联偶合反应中可以容忍多种官能团存在,因而这种通用和高效的铁/铜共催化剂可以广泛用于含有(芳基)C-N或(芳基)C-O(芳基)键的化合物合成中。实验结果表明,卤代芳烃的活性顺序依次为:碘代物>溴代物>氯代物,脂肪胺的活性要高于芳香胺。含有吸电子基团卤代芳烃活性高于给电子基团卤代芳烃,位阻效应的存在会使反应活性稍有所降低。
建立了一种铁催化的烯烃氨溴化的方法。该方法使用FeCl_2作为催化剂,NBS作为溴源,乙酸乙酯作为溶剂,烯烃的氨溴化能在非常温和的条件下高效地进行。这种廉价、高效的催化剂/溴源(FeCl_2/NBS)系统使烯烃的1,2-功能化具有实用价值。实验结果表明,烯烃结构对反应的活性起决定性作用,取代基数量越少、取代基基团越小,反应的活性越高。
建立了一种廉价和空气稳定的FeCl_2/NBS催化体系,高效地催化苄基sp~3杂化的C-H键酰胺化方法。该方法使用FeCl_2作为催化剂, NBS作为氧化剂,乙酸乙酯作为溶剂,在温和条件下酰胺化产率较高。该反应对空气中的湿气和氧气不敏感,也无需干燥的溶剂或惰性环境保护。这种廉价易得的催化/氧化剂(FeCl_2/NBS)体系使未活化的C-H键的酰胺化具有实用价值。
Many natural products, drugs and dyes contain C-N, C-O bonds, so the transition metal-catalyzed construction of C-N, C-O bonds is an effective strategy. The iron and copper salts are applied to catalyze organic reactions for their low price and toxicity. In this dissertation, some iron catalysts and iron/copper co-catalysts were used in Ullmann N- and O-arylations, aminohalogenation of alkenes and amidation of C-H bonds, and some important results were obtained as follows:
We have developed an efficient and inexpensive bimetallic catalyst FeCl_3/CuO/rac-BINOL that could greatly promote N, O-arylation of aliphatic, aryl amines and phenols, and the cross-coupling reactions were of tolerance of various functional groups, so the versatile and efficient iron/copper-co-catalyst can widely be used in the synthesis of the compounds containing the (aryl)C-N or (aryl)C-O(aryl) bond.
We have developed an iron-catalyzed method for aminobromination of alkenes, the protocol uses FeCl_2 as the catalyst, NBS as the halogen source, ethyl acetate as the solvent, and the aminobrominations were efficiently performed under very mild conditions. The direct 1,2-functionalization of alkenes by inexpensive and convenient catalyst-bromine source (FeCl_2/NBS) system is of practical applications.
We have developed an efficient, inexpensive and air-stable FeCl_2/NBS-mediated amidation of benzylic sp~3 C-H bonds; the protocol uses FeCl_2 as the catalyst, non-explosive NBS (compared with the usual oxidants) as the oxidant, ethyl acetate as the solvent, and the amidation provided the reasonable yields under mild conditions. The reactions are insensitive to atmospheric moisture and oxygen, and neither dried solvent nor an inert atmosphere is required. The inexpensive and readily available catalyst-oxidant (FeCl_2/NBS) system is of practical applications for amidation of the unactivated C-H bonds.
建立了一种高效、廉价的双金属催化剂FeCl_3/CuO/消旋化的BINOL,可以极大的催化脂肪胺、芳基胺和酚的N、O-芳基化,而且在交联偶合反应中可以容忍多种官能团存在,因而这种通用和高效的铁/铜共催化剂可以广泛用于含有(芳基)C-N或(芳基)C-O(芳基)键的化合物合成中。实验结果表明,卤代芳烃的活性顺序依次为:碘代物>溴代物>氯代物,脂肪胺的活性要高于芳香胺。含有吸电子基团卤代芳烃活性高于给电子基团卤代芳烃,位阻效应的存在会使反应活性稍有所降低。
建立了一种铁催化的烯烃氨溴化的方法。该方法使用FeCl_2作为催化剂,NBS作为溴源,乙酸乙酯作为溶剂,烯烃的氨溴化能在非常温和的条件下高效地进行。这种廉价、高效的催化剂/溴源(FeCl_2/NBS)系统使烯烃的1,2-功能化具有实用价值。实验结果表明,烯烃结构对反应的活性起决定性作用,取代基数量越少、取代基基团越小,反应的活性越高。
建立了一种廉价和空气稳定的FeCl_2/NBS催化体系,高效地催化苄基sp~3杂化的C-H键酰胺化方法。该方法使用FeCl_2作为催化剂, NBS作为氧化剂,乙酸乙酯作为溶剂,在温和条件下酰胺化产率较高。该反应对空气中的湿气和氧气不敏感,也无需干燥的溶剂或惰性环境保护。这种廉价易得的催化/氧化剂(FeCl_2/NBS)体系使未活化的C-H键的酰胺化具有实用价值。
Many natural products, drugs and dyes contain C-N, C-O bonds, so the transition metal-catalyzed construction of C-N, C-O bonds is an effective strategy. The iron and copper salts are applied to catalyze organic reactions for their low price and toxicity. In this dissertation, some iron catalysts and iron/copper co-catalysts were used in Ullmann N- and O-arylations, aminohalogenation of alkenes and amidation of C-H bonds, and some important results were obtained as follows:
We have developed an efficient and inexpensive bimetallic catalyst FeCl_3/CuO/rac-BINOL that could greatly promote N, O-arylation of aliphatic, aryl amines and phenols, and the cross-coupling reactions were of tolerance of various functional groups, so the versatile and efficient iron/copper-co-catalyst can widely be used in the synthesis of the compounds containing the (aryl)C-N or (aryl)C-O(aryl) bond.
We have developed an iron-catalyzed method for aminobromination of alkenes, the protocol uses FeCl_2 as the catalyst, NBS as the halogen source, ethyl acetate as the solvent, and the aminobrominations were efficiently performed under very mild conditions. The direct 1,2-functionalization of alkenes by inexpensive and convenient catalyst-bromine source (FeCl_2/NBS) system is of practical applications.
We have developed an efficient, inexpensive and air-stable FeCl_2/NBS-mediated amidation of benzylic sp~3 C-H bonds; the protocol uses FeCl_2 as the catalyst, non-explosive NBS (compared with the usual oxidants) as the oxidant, ethyl acetate as the solvent, and the amidation provided the reasonable yields under mild conditions. The reactions are insensitive to atmospheric moisture and oxygen, and neither dried solvent nor an inert atmosphere is required. The inexpensive and readily available catalyst-oxidant (FeCl_2/NBS) system is of practical applications for amidation of the unactivated C-H bonds.
引文
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