共查询到19条相似文献,搜索用时 93 毫秒
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以合成的两组手性催化剂,(S)-二苯基脯氨醇(1)和(2S)-(二苯基羟甲基)-4苯氧基-四氢吡咯(2),(R)-2-氨基-1,1-二苯基-3.(2’-萘基)-1-丙醇(3)和(R)-1-(1’-氨基-2’-萘乙基)-环戊醇(4),用于六种前手性酮的不对称硼烷还原反应,比较其还原结果,发现(2)的性能优于(1),(4)优于(3)。因此认为催化剂中取代基的引入以及含有刚性骨架均有利于对映选择性的提高。 相似文献
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手性含硫恶唑硼烷催化芳酮不对称还原反应的量子化学研究 总被引:1,自引:0,他引:1
用HF方法在6-31G^*基组下,对手性含硫恶唑硼烷催化苯乙酮不对称还原反应进行了量子化学从头算研究。还原反应经历了催化剂-硼烷加合物、催化剂-硼烷-酮加合物、催化剂-烷氧基硼烷加合物的生成以及催化剂-烷氧基硼烷加合物的离解过程。催化剂-硼烷加合物、催化剂-硼烷-酮加合物和催化剂-烷氧基硼烷加合物的生成分别为放热、吸热、放热过程;催化剂-烷氧基硼烷加合物离解成催化剂烷氧基硼烷为吸热过程。催化剂-硼烷-酮加合物和催化剂-烷氧基硼烷加合物都存在四种稳定的结构。最有利于氢转移的催化剂-硼烷-酮加合物结构是次低能量结构,并且具有扭曲的船形结构。催化剂-烷氧基硼烷加合物含有一个B-O-B-N四元环,尽管四元环有较大的张力,但加合物仍有较高的稳定性。 相似文献
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对手性唑硼烷催化3,3-二甲基丁酮-2不对称还原反应机理进行了从头算研究.结果表明,该不对称还原反应是放热的.反应经历了催化剂-硼烷加合物、催化剂-硼烷-酮加合物、含B-O-B-N四元环的催化剂-烷氧基硼烷加合物的生成,以及催化剂-烷氧基硼烷加合物的离解并再生催化剂等过程.在催化剂-硼烷-酮加合物经氢转移而生成催化剂-烷氧基硼烷加合物的过程中,氢转移与B-O-B-N四元环的形成是协同进行的.氢转移是还原反应的控制步骤.氢转移过渡态具有扭曲的椅式结构,所决定的还原产物是与实验相吻合的R手性醇. 相似文献
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对手性噁唑硼烷催化3,3-二甲基丁酮-2不对称还原反应机理进行了从头算研究.结果表明,该不对称还原反应是放热的.反应经历了催化剂-硼烷加合物、催化剂-硼烷-酮加合物、含B-O-B-N四元环的催化剂-烷氧基硼烷加合物的生成,以及催化剂-烷氧基硼烷加合物的离解并再生催化剂等过程.在催化剂-硼烷-酮加合物经氢转移而生成催化剂-烷氧基硼烷加合物的过程中,氢转移与B-O-B-N四元环的形成是协同进行的.氢转移是还原反应的控制步骤.氢转移过渡态具有扭曲的椅式结构,所决定的还原产物是与实验相吻合的R手性醇. 相似文献
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Quantum chemical study on the mechanism of enantioselective reduction of prochiral ketones catalyzed by oxazaborolidines 总被引:1,自引:0,他引:1
The ab initio molecular orbital study on the mechanism of enantioselective reduction of 3,3-dimethyl butanone-2 with borane catalyzed by chiral oxazaborolidine is performed. As illustrated, this enantioselective reduction is exothermic and goes mainly through the formations of the catalyst-borane adduct, the catalyst-borane-3,3-dimethyl butanone-2 adduct, and the cata-lyst-alkoxyborane adduct with a B-O-B-N 4-member ring and through the decomposition of the catalyst-alkoxyborane adduct with the regeneration of the catalyst. During the hydride transfer in the catalyst-borane-3,3-dimethyl butanone-2 adduct to form the catalyst-alkoxyborane adduct, the hydride transfer and the formation of the B-O-B-N 4-member ring in the catalyst-alkoxyborane adduct happen simultaneously. The controlling step for the reduction is the transfer of hydride from the borane moiety to the carbonyl carbon of 3,3-dimethyl butanone-2. The transition state for the hydride transfer is a twisted chair structure and the reduction leads to 相似文献
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Easily available D-(+)-camphor-derived chiral mercapto-alcohols 2 and 3 were employed for catalytic asymmetric borane reduction of aromatic ketones. Moderate enantioselectivities with e.e. 20.2-72.1% were obtained with 10 mol% catalyst. Opposite asymmetric induction was achieved when mercapto-alcohols 2 and 3 were used. 相似文献
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《Tetrahedron letters》1988,29(35):4453-4456
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Kang‐Ying Li Zheng‐Hong Zhou Li‐Xin Wang Guo‐Feng Zhao Michael C. K. Choi Qi‐Lin Zhou Chu‐Chi Tang 《Heteroatom Chemistry》2003,14(3):288-291
Synthesis of several new chiral phosphinamide catalysts with a proximal hydroxyl group from L ‐serine was described. These compounds have been successfully used in the asymmetric catalytic borane reduction of prochiral ketones. The optically active secondary alcohols were obtained with an enantiomeric excess (ee) up to 81% and excellent yields. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:288–291, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10145 相似文献
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A series of bis-hydroxyamides were synthesized from diphenylamine-2,2′-dicarboxylic acid and chiral aminoalcohols. Their catalytic activity in asymmetric borane reduction was investigated. After the fine optimization of solvents, temperature, amount of borane complex, and the length of catalyst generating period, good to excellent yields (55–99%) and enantioselectivities (79–97% ee) can be achieved in the reduction of aromatic and alkyl prochiral ketones. A transition state structure was proposed on the basis of absolute configuration and controlled experiment. 相似文献
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《Tetrahedron: Asymmetry》2006,17(12):1895-1900
A novel sulfonamide catalyst based on a room temperature ionic liquid (RTIL) has been developed for the enantioselective reduction of ketones in refluxing toluene. The optically active secondary alcohol products were obtained in good enantiomeric excess and excellent yields. The imidazolium-tagged sulfonamide catalyst can be readily recovered and reused four times without any significant loss of catalytic activity. 相似文献