邢爱萍.溴化钯或乙酰丙酮羰基铑/手性配体催化醛与乙酰胺的不对称酰胺羰化反应研究[J].分子催化,2011,(3):202-208
溴化钯或乙酰丙酮羰基铑/手性配体催化醛与乙酰胺的不对称酰胺羰化反应研究
Asymmetric Amidocarbonylation of Aldehyde and Acetamide Catalyzed by Chiral Palladium or Rhodium Complexes
投稿时间:2011-04-25  修订日期:2011-05-24
DOI:
中文关键词:  溴化钯  乙酰丙酮羰基铑  环己基甲醛  苯乙醛  手性配体  不对称酰胺羰化
英文关键词:Palladiumbromide  acetylacetonatodicarbonyl rhodium  Cyclohexanecarboxaldehyde  Phenylacetaldehyde  Chiral phosphine and phosphite ligands  Asymmetric amidocarbonylation
基金项目:国家自然科学基金项目(面上项目,重点项目,重大项目)
作者单位E-mail
邢爱萍* 中国科学院兰州化学物理研究所 hn_xap@163.com 
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中文摘要:
      采用溴化钯为催化剂前体,与非螯合型双齿膦配体L1(DPPFF)、联吡啶型双齿膦配体L2(P-PHOS)和二茂铁基手性双膦配体L3((S,Rp)-BPPF) 制备络合物催化剂,以乙酰丙酮羰基铑为催化剂前体,与手性亚磷酸酯配体L4-L6制备络合物催化剂,将其分别应用于底物环己基甲醛或苯乙醛的不对称酰胺羰化反应中,研究结果表明,溴化钯与联吡啶型双齿膦配体L2络合物催化剂在苯乙醛的酰胺羰化反应中给出25%ee和11%的产率;溴化钯与非螯合型双齿膦配体L1络合物催化剂在环己基甲醛反应中给出4.3%ee和15%的产率。
英文摘要:
      The in situ prepared chiral catalyst of Pd / unchelating bidentate phosphine ligand L1 (DPPFF), bipyridine bidentate phosphine ligand L2 (P-PHOS), and bidentate phosphine ligand L3 ((S, Rp)-BPPF), and Rh / phosphite ligands L4 –L6, have been applieded in amidocarbonylation of cyclohexanecarboxaldehyde or phenylacetaldehyde. Pd / bipyridine bidentate phosphine ligand L2 gave the enantioselectivity 25% (S) and the yield 11% in amidocarbonylation of phenylacetaldehyde ,When Pd / unchelating bidentate phosphine ligand L1 was employed in asymmetric amidocarbonylation of cyclohexanecarboxaldehyde, the enantioselectivity 4.3% (S) and the yield 15% were received.
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