Development of Asymmetric Selenoxide and Telluroxide Elimination.

不对称氧化硒和氧化碲消除的发展。

• 批准号: 04453086
• 负责人: UEMURA Sakae
• 金额: $ 4.61万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General 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/en/grant/KAKENHI-PROJECT-04453086/
• 关键词: asymmetric synthesis; selenoxide elimination; telluroxide elimination; Chiral compound; [2,3]sigmatropic rearrangement; binaphthol; Sharpless oxidant; Davis oxidant

We succeeded in asymmetric selenoxide elimination leading to chiral allenic sulfones and chiral alkyl and aryl cyclohexylidenemethyl ketones by oxidation of the corresponding selenides with chiral oxidants such as Sharpless oxidant and Davis oxidant. In the former case the maximum enatioselectivity was 42%ee, while in the latter case it reached to 83%ee. The nature of alkyl or aryl group of RSe or ArSe moiety had a remarkable effect on the ee value. On the other hand, we have not yet succeeded in asymmetric telluroxide elimination. In connection to these asymmetric reactions we were also successful in catalytic asymmetric oxidation of sulfides to sulfoxides with t-BuOOH using binaphthol as a chiral auxiliary and kinetic resolution of sulfoxides catalyzed by chiral titanium-binaphtholcomplex. Furthermore, we found that the Sharpless oxidation of some aryl cinnamyl selenides afforded a chiral 1-pheny1-2-propen-1-ol via asymmetric[2,3]sigmatropic rearrangement in a moderate to high selectivity(up to 92%ee).

我们通过用手性氧化剂（例如 Sharpless 氧化剂和 Davis 氧化剂）氧化相应的硒化物，成功地实现了不对称二氧化硒消除，从而产生了手性联二烯砜和手性烷基和芳基亚环己基甲基酮。在前一种情况下，最大对映选择性为 42%ee，而在后一种情况下，它达到 83%ee。 RSe或ass部分的烷基或芳基的性质对ee值有显着影响。另一方面，我们尚未成功消除不对称碲氧化物。与这些不对称反应相关，我们还成功地使用联萘酚作为手性助剂，用t-BuOOH将硫化物催化不对称氧化为亚砜，并在手性钛-联萘酚络合物催化下动力学拆分了亚砜。此外，我们发现一些芳基肉桂基硒化物的Sharpless氧化通过不对称[2,3]σ重排以中等到高选择性（高达92％ee）提供手性1-苯基1-2-丙烯-1-醇。

项目成果

N.Komatsu et al.: "Kinetic Resolution of Sulfoxides Catalyzed by Chiral Titanium-Binaphthol Complex" J.Org.Chem.58. 7624-7626 (1993)

N.Komatsu 等人：“手性钛-联萘酚复合物催化亚砜的动力学拆分”J.Org.Chem.58。

Naoki Komatsu: "Asymmetric Selenoxide Elimination Leading to Chiral Allenic Sulfones" J.Org.Chem.58. 3697-3702 (1993)

Naoki Komatsu：“不对称氧化硒消除导致手性艾伦磺酸”J.Org.Chem.58。

Yoshiaki Nishibayashi: "Telluroxide Elimination by Oxidation of Alkyl Aryl Tellurides: A Remarkable Effect of Triethylamine Added" J.Chem.Soc.,Perkin 1. (1993)

Yoshiaki Nishibayashi：“通过烷基芳基碲化物的氧化消除碲氧化物：添加三乙胺的显着效果”J.Chem.Soc.，Perkin 1. (1993)

Naoki Komatsu: "Asymmetric Selenoxide Elimination Leading to Chiral Allenic" J.Org.Chem.58. 3697-3702 (1993)

Naoki Komatsu：“不对称氧化硒消除导致手性艾伦酸”J.Org.Chem.58。

Naoki Komatsu: "Advances in Detailed Reaction Mechanisms" Ed.by J.M.Coxon;JAI press,England,UK(in press), (1994)

Naoki Komatsu：“详细反应机制的进展”，J.M.Coxon 编着；JAI 出版社，英国，英格兰（正在出版），（1994 年）