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以甘露醇和山梨醇为原料,合成了2个新的手性膦配体,并用这些新的手性膦配体与钯原位生成的催化剂体系催化苯乙烯的不对称氢酯基化反应,得到R构型的2-苯基丙酸甲酯,其ee值分别为28.5%和13.6%。 相似文献
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通过手性二胺配体与Cu或Ni络合合成了手性金属催化剂,并将其应用于α-酮酸酯对硝基烯的不对称共轭加成反应中,发展了通过改变中心金属或调节配体刚性实现反应对映选择性反转的策略.使用同一手性二胺配体(1S,1'S)-1,1'-联异吲哚啉,与不同的金属前体(Cu(OAc)2·H2O与Ni(OAc)2·4H2O)络合,可以高选择性地得到绝对构型相反的共轭加成产物(ee值高达94%与93%).同样,使用同一金属前体Cu(OAc)2·H2O,与同一手性源出发合成的两种刚性不同的二胺配体络合,也可以在这个反应中实现产物绝对构型的反转(ee值高达94%与94%). 相似文献
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氮杂环丙烷作为环氧丙烷的结构类似物,表现出与后者类似的亲电反应性[1],是重要的有机合成中间体.近十年来,通过氮宾与双键的加成合成手性氮杂环丙烷也得到了一定的发展[2,3],我们用以蒽为骨架的新型手性双噁唑啉配体AnBox(1)对一系列α,β-不饱和酮进行高对映选择性地氮杂环丙烷化,反应的收率可以达到92%,ee值达到>99%,远高于文献中报道的ee值(86%)[4].同时通过与Evans的配体Box(2)比较发现,从相同构型的氨基醇得到的手性双噁唑啉催化相同底物的氮杂环丙烷化时得到相反绝对构型的产物,这两个不同骨架的配体形成的手性环境的差异对这种立体构型的翻转起着重要作用. 相似文献
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手性膦配体及其不对称催化的研究进展①徐小红吕士杰傅宏祥(中国科学院兰州化学物理研究所,兰州730000)关键词膦配体手性配体不对称催化1前言手性是宇宙间的普遍特性,在生命的产生和演变过程中,自然界往往对一种手性有所偏爱.如:自然界存在的糖为D构型,氨... 相似文献
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中药麻黄中的植物碱主要是D-(-)-麻黄碱(ephedrine)和L-( )-伪麻黄碱(Pseudoephedrine),人们以此为手性源合成了许多优秀的手性配体并在反应中取得了很好的结果[1].我们以此为手性源很方便地合成了新型的具有三手性中心的磺酰胺-胺醇类配体(Scheme 1).基于配体的特点,将其应用于催化二乙基锌对芳香醛的不对称加成反应,取得了很高的收率和好的对映选择性,产物的绝对构型都为(S)-型.令人惊奇的是,在该反应体系中加入Ti(OPr-i)4,发现此类配体也能表现出较好的结果,产物的绝对构型都是(R)-型. 相似文献
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《Tetrahedron: Asymmetry》2006,17(5):742-749
Novel norephedrine-based chiral ligands with multiple stereogenic centers were conveniently prepared from norephedrine and N-substituted pyrrole. These novel chiral ligands were used to catalyze the enantioselective addition of diethylzinc to aldehydes and to chalcone in high yields and with good to high enantioselectivities. The absolute configuration of products was found to be affected by the stereogenic centers on the norephedrine part of the novel chiral ligands. 相似文献
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金鸡纳生物碱的金属络合物用于苯乙酮的不对称催化还原 总被引:3,自引:0,他引:3
金鸡纳生物碱的金属络合物用于苯乙酮的不对称催化还原刘湘(无锡轻工大学化工系无锡214036)李纪国张正(南京大学化学系南京210093)关键词金鸡纳生物碱手性络合物不对称还原苯乙酮分类号O643.32近10多年来,前手性酮的不对称还原反应作为制备光学... 相似文献
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The design of new chiral ligands is the key in the development of transition metal catalyzed asymmetric synthesis. Many chiral diphosphine ligands have been prepared and applied in asymmetric catalytic reactions with excellent enantioselectivities. Among the chiral diphosphine ligands that have been reported, the atropisomeric C2-symmetric phosphines with a biaryl scaffold initiated by Noyori and co-workers with BINAP were found to have the widest application in the transition metal catalyze… 相似文献
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不对称催化是有机化学研究的前沿领域和发展方向.近10年来,手性配体的研究得到了长足的发展,大量的小分子手性配体被报道,其中许多手性配体展示了优异的催化性能.但是由于昂贵的手性配体(金属催化剂)分离、回收和再利用的问题,从而限制了小分子催化剂的应用.因此,解决手性金属催化剂的分离与回收问题是不对称催化研究领域的一个热点问题.为了解决这一关键问题,国内外科学家从负载的角度出发已经成功地发展了众多的研究方法,无机负载法、交联高分子负载法、可溶性高分子负载法、树状大分子负载法等.许多负载的手性金属催化剂已经表现出优异的催化活性和高的对映选择活性. 相似文献
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Muralidhara Thimmaiah 《Journal of organometallic chemistry》2007,692(10):1956-1962
Four benzoferrocenyl phosphorus chiral ligands were conveniently prepared in good overall yields. These ligands were found to be stable in solid form and in solution. Two of the four ligands were resolved by chiral HPLC. Unlike a reported bis(phosphino-η5-indenyl)iron(II) complex, in which the indenyl ligands undergo ring flipping through an η1-intermediate, these two ligands were found to be configurationally stable in solution and in solid state. The suitability of these ligands for enantioselective catalysis was assessed in studies on allylic alkylation reactions. When the two less sterically hindered ligands were used, excellent chemical yields were obtained, but the other two more sterically hindered ones gave lower yields. When the two enantiopure ligands were used, enantioselectivity of up to 51% ee was observed. These findings suggest that benzoferrocene derivatives may be used as chiral ligands for asymmetric catalysis. 相似文献
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Thaler T Guo LN Steib AK Raducan M Karaghiosoff K Mayer P Knochel P 《Organic letters》2011,13(12):3182-3185
Sulfoxide-alkene hybrids are introduced as a new class of chiral heterodentate ligands for the Hayashi-Miyaura reaction. The synthesis of these ligands was achieved without the use of protecting groups. A chiral resolution was performed via simple column-chromatographic separation of the diastereomeric ligands. Both diastereomers proved to be excellent ligands in Rh-catalyzed 1,4-addition reactions, furnishing chiral products with high enantioselectivities and, remarkably, opposite stereoconfigurations. 相似文献