Development of Selective Oxidation of Alkenes by Heterometallic Catalysts and Its Synthetic Application

异金属催化剂选择性氧化烯烃的研究进展及其合成应用

• 批准号: 04555206
• 负责人: MURAHASHI Shun-Ichi
• 金额: $ 6.85万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-04555206/
• 关键词: Allylic Compounds; Aldehydes; Asymmetric Acetalization; 1beta-Methylcarbapenem; Isoxazolidines; Hydroxylation; Hydroxyketones; パラジウム; ルテニウム; オスミニウム; 不斉ヒドロキシル化

Development of effective, catalytic reactions which are highly controlled in terms of regio-and stereoselectivity is certainly required in the field of synthetic chemistry. Access to this problem is provided by the aid of metal complex catalysts. From such a view point, we have aimed to develop stereo-and regioselective oxidations of alkenes by using heterometallic catalysts. The major results obtained in this study are as follows.1. We have developed palladium(II)-catalyzed asymmetric acetalization of methacrylic derivatives bearing optically active 2-oxazolidinones, from which optically active 3-hydroxy-2-methylpropanal is obtainable in high enantiomer excess. The reaction can be performed in large scale, and the aldehyde obtained was found to serve as a useful building block for the synthesis of an azetizinone derivative of 1beta-methylcarbapenem precursor.2. Treatment of N-allylamides and lactams with molecular oxygen in the presence of a heterometalic catalyst consisting of PdCl_2, CuCl, and hexamethylphosphoric triamide was found to produce the corresponding aldehydes regioselectively. On the other hand, when water is present in the reaction system, it gives the corresponding methyl ketones. There is so far no precedent for such a complete reversal of the regioselectivity in this type of oxidations.

在合成化学领域，开发在区域选择性和立体选择性方面受到高度控制的有效催化反应是必然需要的。金属络合催化剂提供了解决这一问题的途径。从这个角度来看，我们的目标是利用异金属催化剂来发展烯烃的立体和区域选择性氧化。本研究得到的主要结果如下：1。我们已经开发了钯（II）催化的不对称缩醛化的含光学活性2-恶唑烷酮的甲基丙烯酸衍生物，从中得到光学活性3-羟基-2-甲基丙烯高过量的对映体。该反应可以大规模进行，所得到的醛可以作为合成1 - β -甲基碳青霉烯前体氮杂tizinone衍生物的有效组成部分。在由PdCl_2、CuCl和六甲基磷酸三酰胺组成的异金属催化剂存在下，用分子氧处理n -烯丙酰胺和内酰胺可以选择性地生成相应的醛。另一方面，当反应系统中有水存在时，它会生成相应的甲基酮。到目前为止，还没有在这种类型的氧化中完全逆转区域选择性的先例。

项目成果

T.Naota: "Osmium-Catalyzed Oxidative Transformation of Alkenes to -Ketons with Peracetic Acid" Chem.Lett.1767-1770 (1993)

T.Naota：“用过乙酸锇催化烯烃氧化转化为酮” Chem.Lett.1767-1770 (1993)

T.Naota: "Osmium-Catalyzed Oxidative Transformation of Alkenes to α-Ketons with Peracetic Acid" Chem.Lett.1767-1770 (1993)

T.Naota：“用过乙酸锇催化烯烃氧化转化为 α-酮” Chem.Lett.1767-1770 (1993)

Shun-Ichi Murahashi: "Palladium(II)-catalyzed Asymmetric Acetalization of Alkenes." J.Chem.Soc.Chem Comm.117-118 (1993)

Shun-Ichi Murahashi：“钯 (II) 催化的烯烃不对称缩醛化。”

Shun-Ichi Murahashi: "Palladium(II)-catalyzed Oxygenation of the Carbon-Carbon Double Bond by Molecular oxygen." J.Mol.Cat.74. 489-491 (1992)

Shun-Ichi Murahashi：“钯 (II) 催化分子氧对碳-碳双键的氧化。”

Shun-Ichi Murahashi: "Palladium(II)-catalyzed Oxygenation of the Carbon-Carbon Double Bond by Molecular Oxygen:" J.Molecular Catalysis. 74. 489-498 (1992)

Shun-Ichi Murahashi：“分子氧对碳-碳双键的钯 (II) 催化氧化：”J.Molecular Catalysis。