Novel equilibrium control under transition-metal catalysis

过渡金属催化下的新型平衡控制

• 批准号: 22689001
• 负责人: ARISAWA MIEKO
• 金额: $ 19.5万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Young Scientists (A)
• 财政年份: 2010
• 资助国家: 日本
• 起止时间: 2010-04-01 至 2014-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-22689001/
• 关键词: 平衡制御; 触媒反応; 有機イオウ化合物; 切断再配列; へテロ元素捕捉剤; 平衡相関; ロジウム触媒; 単結合メタセシス反応; ヘテロ元素捕捉剤; イオウ単体; C-H活性化置換反応; 不活性結合; 酸性度; 平衡反応; 熱力学的安定性; 単結合

I found that transition-metal complexes could be used as catalyst for the synthesis and transformation of organosulfur compounds, and that a variety of reactions involving cleavage of heteroatom bonds such as C-S, C-F, C-C, C-O, S-S, P-P bonds were developed. The development of efficient catalysts, which decreases the activation energy of the reaction, provides equilibrium reactions, when the relative thermodynamic stabilities of the substrates and products are close. Then, equilibrium control methods using co-substrates and thermodynamically intermediate substrates were developed. Method employing the combination of transition-metal catalysis and equilibrium control can be generally used for the synthesis of organosulfur compounds.

我发现过渡金属复合物可以用作有机硫化合物合成和转化的催化剂，并且开发了各种涉及杂原键的反应，例如C-S，C-C，C-C，C-C，C-O，S-S-S-S，P-P键。当底物和产物的相对热力学稳定性接近时，有效的催化剂的发展可降低反应的活化能，从而提供平衡反应。然后，开发了使用共覆盖物和热力学中间底物的平衡控制方法。采用过渡金属催化和平衡控制的组合的方法通常可用于合成有机硫化合物。

项目成果

Rhodium-Catalyzed Synthesis of Diaryl Sulfides Using Aryl Fluorides and Sulfur/Organopolysulfides

• DOI: 10.1021/ol302497m
• 发表时间: 2012-10-19
• 期刊: ORGANIC LETTERS
• 影响因子: 5.2
• 作者: Arisawa, Mieko;Ichikawa, Takuya;Yamaguchi, Masahiko
• 通讯作者: Yamaguchi, Masahiko

Rhodium-catalyzed α-Methylthiolation Reaction of Unactivated Ketones Using 1,2-Diphenyl-2-methylthio-1-ethanone for the Methylthio Transfer Reagent

使用 1,2-二苯基-2-甲硫基-1-乙酮作为甲硫基转移试剂，铑催化未活化酮的 α-甲硫基化反应

• DOI: 10.1016/j.tet.2011.01.071
• 发表时间: 2011
• 期刊: Tetrahedron
• 影响因子: 2.1
• 作者: M. Arisawa;F. Toriyama;M. Yamaguchi
• 通讯作者: M. Yamaguchi

有機イオウ・リン化合物の触媒的平衡制御合成

有机硫磷化合物的催化平衡控制合成

• 发表时间: 2011
• 作者: Iizuka M;Murata T;Hori M;Ozaki H;有澤 美枝子
• 通讯作者: 有澤 美枝子

Synthesis of unsymmetrical polyfluorinated diaryl sulfides by rhodium-catalyzed aryl exchange reaction

• DOI: 10.1016/j.tetlet.2013.06.021
• 发表时间: 2013-08
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: M. Arisawa;T. Ichikawa;M. Yamaguchi

Synthesis of organosulfides using transition-metal-catalyzed substitution reactions: to construct exergonic reactions employing metal inorganic and organic co-substrate/co-product methods

• DOI: 10.1016/j.tetlet.2014.04.081
• 发表时间: 2014-06
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: M. Arisawa