Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity

Charlie Blons; Marie S. T. Morin; Thibault E. Schmid; Thomas Vives; Sophie Colombel- Rouen; Olivier Baslé; Thibault Reynaldo; Cody L. Covington; Stéphanie Halbert; Sean N. Cuskelly; Paul V. Bernhardt; Craig M. Williams; Jeanne Crassous; Prasad L. Polavarapu; Christophe Crévisy; HélHne Gérard; Marc Mauduit

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Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity

机译：不对称序贯Cu催化的1,6 / 1,4-缀合物加入循环亚酮的硬质核试剂：确定绝对构型和映射性的起源

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The first stereocontrolled Cu-catalyzed sequential 1,6/1,4-asymmetric conjugate addition (ACA) of C-metalated hard nucleophiles to cyclic dienones is reported. The use of DiPPAM (diphenylphosphinoazomethinylate) followed by a phosphoramidite as the stereoinducing ligands facilitated both high ee values for the 1,6-ACA and high de values for the 1,4-ACA reaction components, which thus gave enantioenriched 1,3-dialkylated moieties. The absolute configurations were determined by using vibrational circular dichroism (VCD) and optical rotatory dispersion (ORD) spectroscopy, in combination with DFT calculations and X-ray analysis. Interestingly, DFT calculations for the mechanism of enantioselective 1,6-addition by using an unprecedented Cu–Zn bimetallic catalytic system confirmed this attribution. Lastly, exploring intramolecular cyclization avenues for enantioenriched 1,3-dialkylated products provided access to the challenging drimane skeleton.

机译：据报道，据报道了第一种立体控制Cu催化的序贯1,6 / 1,4-不对称缀合物的C-金属化硬质核试剂对环状烯酮的加入（ACA）。使用Dippam（二苯基膦酰胺甲基丙烯酸甲酯），然后是磷光酰胺，作为立体丁基配体，促进了1,6-ACA和1,4-ACA反应组分的高ee值，从而促进了对雌激发的1,3-二烷基化的部分。通过使用振动圆形二色（VCD）和光学旋转分散（ORD）光谱与DFT计算和X射线分析结合来确定绝对配置。有趣的是，通过使用前所未有的Cu-Zn Bimetallic催化系统对映选择性1,6-添加的机制的DFT计算证实了这种归因。最后，探索对灭菌的1,3-二烷基化产品的分子内环化途径提供了对挑战脱烷骨架的进入。

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《Chemistry: A European journal》 |2017年第31期|共11页
作者
Charlie Blons; Marie S. T. Morin; Thibault E. Schmid; Thomas Vives; Sophie Colombel- Rouen; Olivier Baslé; Thibault Reynaldo; Cody L. Covington; Stéphanie Halbert; Sean N. Cuskelly; Paul V. Bernhardt; Craig M. Williams; Jeanne Crassous; Prasad L. Polavarapu; Christophe Crévisy; HélHne Gérard; Marc Mauduit;
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作者单位

Ecole Nationale Supérieure de Chimie de Rennes CNRS UMR 6226 11 allée de Beaulieu CS 50837 35708 Rennes Cedex 7 (France);

Ecole Nationale Supérieure de Chimie de Rennes CNRS UMR 6226 11 allée de Beaulieu CS 50837 35708 Rennes Cedex 7 (France);

Ecole Nationale Supérieure de Chimie de Rennes CNRS UMR 6226 11 allée de Beaulieu CS 50837 35708 Rennes Cedex 7 (France);

Ecole Nationale Supérieure de Chimie de Rennes CNRS UMR 6226 11 allée de Beaulieu CS 50837 35708 Rennes Cedex 7 (France);

Ecole Nationale Supérieure de Chimie de Rennes CNRS UMR 6226 11 allée de Beaulieu CS 50837 35708 Rennes Cedex 7 (France);

Ecole Nationale Supérieure de Chimie de Rennes CNRS UMR 6226 11 allée de Beaulieu CS 50837 35708 Rennes Cedex 7 (France);

Universit8 de Rennes 1 CNRS UMR 6226 Campus de Beaulieu 35042 Rennes Cedex (France);

Department of Chemistry Vanderbilt University Nashville TN 37235 (USA);

Sorbonne Universités UPMC Univ Paris 06 CNRS Laboratoire de Chimie Théorique CC 137 4 place Jussieu F. 75252 Paris Cedex 05 (France);

School of Chemistry and Molecular Biosciences The University of Queensland Brisbane QLD 4072 (Australia);

School of Chemistry and Molecular Biosciences The University of Queensland Brisbane QLD 4072 (Australia);

School of Chemistry and Molecular Biosciences The University of Queensland Brisbane QLD 4072 (Australia);

Universitó de Rennes 1 CNRS UMR 6226 Campus de Beaulieu 35042 Rennes Cedex (France);

Department of Chemistry Vanderbilt University Nashville TN 37235 (USA);

Ecole Nationale Supérieure de Chimie de Rennes CNRS UMR 6226 11 allée de Beaulieu CS 50837 35708 Rennes Cedex 7 (France);

Sorbonne Universités UPMC Univ Paris 06 CNRS Laboratoire de Chimie Théorique CC 137 4 place Jussieu F. 75252 Paris Cedex 05 (France);

Ecole Nationale Supérieure de Chimie de Rennes CNRS UMR 6226 11 allée de Beaulieu CS 50837 35708 Rennes Cedex 7 (France);

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正文语种 eng
中图分类应用化学;
关键词
asymmetric catalysis; circular dichroism; configuration determination; conjugate addition; copper;

机译：不对称催化;圆形二色性;配置确定;共轭添加;铜;

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专利

1. Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity [J] . Charlie Blons, Marie S. T. Morin, Thibault E. Schmid, Chemistry: A European journal . 2017,第31期

机译：不对称序贯Cu催化的1,6 / 1,4-缀合物加入循环亚酮的硬质核试剂：确定绝对构型和映射性的起源
2. Remote Construction of Chiral Vicinal Tertiary and Quaternary Centers by Catalytic Asymmetric 1,6-Conjugate Addition of Prochiral Carbon Nucleophiles to Cyclic Dienones [J] . Wei Yuan, Liu Zunwu, Wu Xinxin, Chemistry: A European journal . 2015,第52期

机译：催化不对称的1,6-共轭手性碳亲核试剂与环状二烯酮的手性三级和四级中心的远程构建
3. Remote Construction of Chiral Vicinal Tertiary and Quaternary Centers by Catalytic Asymmetric 1,6-Conjugate Addition of Prochiral Carbon Nucleophiles to Cyclic Dienones [J] . Wei Yuan, Liu Zunwu, Wu Xinxin, Chemistry: A European journal . 2015,第52期

机译：催化不对称的1,6-共轭手性碳亲核试剂与环状二烯酮的手性三级和四级中心的远程构建
4. Designation of Chiral p, n Ligands in Cu-catalyzed Enantioselective Conjugate Additions [C] . Yuanchun Hu, Xinquan Hu, Junwei Wang, Asia-Pacific Congress on Catalysis . 2003

机译：Cu催化对映选择性缀合物添加中的手性P，N配体的指定
5. Determination of the Absolute Configuration of β-Chiral Primary Alcohols Using the Competing Enantioselective Conversion Method Heteroatom-directed Acylation of Secondary Alcohols to Assign Absolute Configuration Total Synthesis of Illisimonin a Osmate Es [D] . Burns, Alexander Sunshine. 2020

机译：使用竞争对映选择性转化法测定β-chiral初级醇的绝对构型次原子为仲醇的酰化酰化，分配绝对构型Illisimonin的总合成渗透
6. NHC–Cu-Catalyzed Silyl Conjugate Additions to Acyclic and Cyclic Dienones and Dienoates. Efficient Site- Diastereo- and Enantioselective Synthesis of Carbonyl-Containing Allylsilanes [O] . Kang-sang Lee, Hao Wu, Fredrik Haeffner, -1

机译：NHC铜催化的甲硅烷共轭加成以无环和环状烯酮和Dienoates。高效的站点 - Diastereo-和不对称合成羰基含烯丙基硅烷的
7. Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity [O] . Blons, Charlie, Morin, Marie S. T., Schmid, Thibault E., 2017

机译：硬核亲核剂对环二烯的不对称顺序铜催化1,6 / 1,4-共轭加成：绝对构型和对映选择性的起源的确定

Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity

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