Discovery of new function of organophosphorus compounds and their applications to catalytic asymmetric synthesis

有机磷化合物新功能的发现及其在催化不对称合成中的应用

• 批准号: 24659002
• 负责人: HAMADA Yasumasa
• 金额: $ 2.41万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Challenging Exploratory Research
• 财政年份: 2012
• 资助国家: 日本
• 起止时间: 2012-04-01 至 2014-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-24659002/
• 关键词: anionic ligand; phenyl phosphine; phosphide; disproportionation; sulfur; phosphorus; new reaction; tosyl chloride; ホスフィド; 配位子; リン; イオウ; ホスフィン; トシルクロリド; 不均斉化反応; 酸化還元反応; 触媒的合成; 有機合成化学; スルホニルホスフィド; 不斉合成

We focused on phosphide compounds like a sulfonamide as a precursor of an anionic ligand, which have never been reported to date. We first examined the reaction of phenyl phosphine. But no phosphide was obtained. Then, we examined the experiments to corroborate the known procedure using diphenylphosphine and tosyl chloride. Surprisingly, we obtained tolylthiooxydiphenylphosphine oxide instead of the expected phosphide. Based on the results, we re-examined the reaction of phenylphosphine with tosyl chloride, which afforded phenylthiophosphonic acid phenyl thioester. Interestingly, this reaction is a completely new reaction through disproportionation reaction between sulfur and phosphorus. Next, we focused on the reaction of phenyl phosphine with acylating agents. When phosphine borane instead of phosphine, the desired phosphide was isolated as a borane complex. Now we are examining the removal of the borane from the product.

我们专注于磷化合物，如磺酰胺作为阴离子配体的前体，这是迄今为止从未报道过的。我们首先考察了苯基膦的反应。但没有得到磷化物。然后，我们检查了实验以证实使用二苯基膦和甲苯磺酰氯的已知程序。令人惊讶的是，我们获得了甲苯基硫代氧基二苯基氧化膦，而不是预期的磷化物。在此基础上，我们重新考察了苯基膦与对甲苯磺酰氯的反应，得到了苯硫代膦酸苯硫酯。有趣的是，该反应是一个全新的反应，通过硫和磷之间的反硝化反应。接下来，我们重点研究了苯基膦与酰化剂的反应。当膦硼烷代替膦时，所需的磷化物作为硼烷络合物分离。现在我们正在研究从产品中除去硼烷。

项目成果

千葉大学大学院薬学研究院薬化学研究室投稿論文

千叶大学药学院研究生院药物化学实验室提交的论文