Development of Novel Stereoselective Pinacol Coupling Reactions

新型立体选择性频哪醇偶联反应的发展

• 批准号: 12450365
• 负责人: TAKAI Kazuhiko
• 金额: $ 9.6万
• 依托单位: OKAYAMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12450365/
• 关键词: Pinacol Coupling Reaction; Chromium(II); One-Electro Reduction; α,β-Unsaturated Ketone; Allylic Chromium Reagent; Titanium(III) Complex; 1,2-Diol; Low-Valent Metal; ピナコール反応; 交差カップリング反応; マンガン; 立体化学制御; 低原子価チタン; 3価チタン錯体

The following stereoselective pinacol-type reactions are developed. (1) A cross-pinacol-type coupling reaction of α,β-unsaturated ketones and aldehydes is accomplished with CrCl_2 and Me_3SiCl in DMF. The diastereoselectivity of the reaction is proved to depend on the reaction temperature. (2) A cross-coupling reaction of oxygen-substituted dienes and aldehydes leading to 1,2-diol derivatives is performed with CrCl_2 in the presence of a catalytic amount of B_<12> and water. (3) A dl-selective pinacol-coupling reaction of aliphatic aldehydes is achieved with CrCl_2, manganese, and Me_3SiCl.In addition, we collected information on the pinacol coupling reactions with low-valent metals. (1) A titanium(III) complex TiCl_3(tmeda)(thf) which is effective for a dl-selective pinacol-coupling of aromatic aldehydes, is isolated, and the molecular structure of the complex are examined by X-ray crystallographic analysis. (2) Titanium(III) and vanadium(III) complexes having a Tp ligand are isolated, and the structure of an aldehyde-coordinated vanadium(III) complex is determined by X-ray crystallographic analysis.

发展了以下立体选择性pinacol型反应。(1)在DMF中，与CrCl_2和Me_3SiCl发生了α、β-不饱和酮和醛的交叉蒎醇型偶联反应。证明了反应的非对映选择性与反应温度有关。(2)在B_<12>的催化量和水的存在下，用CrCl_2进行了氧取代二烯与醛的交叉偶联反应，生成了1,2-二醇衍生物。(3)脂族醛与CrCl_2、锰和Me_3SiCl进行了dl选择性蒎醇偶联反应。此外，我们还收集了pinacol与低价金属偶联反应的相关信息。(1)分离出一种可选择性偶联芳香醛的钛（III）配合物TiCl_3(tmeda)(thf)，并通过x射线晶体分析对配合物的分子结构进行了表征。(2)分离了具有Tp配体的钛（III）和钒（III）配合物，并通过x射线晶体学分析确定了醛配位钒（III）配合物的结构。