Generations of Organometallic Species by Novel Reduction Reactions and their Applieations to Organic Synthesis

新型还原反应生成有机金属物种及其在有机合成中的应用

• 批准号: 06650975
• 负责人: HOJO Makoto
• 金额: $ 1.34万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06650975/
• 关键词: Ate-complex; Manganese; Silicon; Samarium; Carbonyl Ylid; カルボニルイリド; マンガン; ケイ素; カルボニルイド; 金属-ハロゲン交換

1. Copper ate-complexes serve as reductants and (E) -and (Z) -vinylcopper reagents can be prepared directly. (Chem.Lett.1994,437 ; Bull.Chem.Soc., Jpn.1994,67,1495.) Functionalized allylcopper reagents were also prepared selectively. (J.Chem.Soc., Chem.Commun.1994,2687.) Manganese ate-complexes react with alpha-holoketones to generate enolates of the parent ketones efficiently. Using these reactions, regioselectivities in alkylation and aldol reaction are controlled perfectly. (in preparation)2. Reactivities of oxiranylallylsilanes, aminosilanes, thiomethylsilanes, and alkoxyhydrosilanes were investigated. (J.Organometal.Chem.1994,473, C1 ; Chem.Lett.1994,719 ; Heteroatom Chem.1994,5,229 ; Tetrahedron Lett.1995,36,571 ; Bull.Soc.Chim.Fr.1995,132,499.) (J.Organometal.Chem.1995,499,155.)3. Novel methods for generation of non-stabilized carbonyl ylids were found. (J.Am.Chem.Soc.1996,118, in press ; Synlett, 1996, in press.)

1.铜配合物用作还原剂，并且可以直接制备（E）-和（Z）-乙烯基铜试剂。（Chem.Lett.1994，437; Bull.Chem.Soc.，Jpn.1994，67，1495.）还选择性地制备了功能化的烯丙基铜试剂。（J.Chem.Soc.，Chem.Commun.1994，2687.）锰配合物与α-全酮反应，有效地生成母体酮的烯醇化物。利用这些反应，烷基化反应和羟醛缩合反应的区域选择性得到了很好的控制。(in制备）2.研究了环氧乙烷基烯丙基硅烷、氨基硅烷、硫代甲基硅烷和烷氧基氢硅烷的反应性。（J.Organometal.Chem.1994，473，C1 ; Chem.Lett.1994，719; Heteroatom Chem.1994，5，229; Tetrahedron Lett.1995，36，571; Bull.Soc.Chim.Fr.1995，132，499.）（J.Organometal.Chem.1995，499，155。）3.发现了产生不稳定的羰基叶立德的新方法（J. Am. Chem. Soc. 1996，118，出版中; Synlett，1996，出版中）。

项目成果

Makoto Hojo, Naruyasu Ishibashi, and Akira Hosomi: "Heteroarylthiomethylsilanes. Synthesis and Application to Heteroarylthiomethylation of Carbonyl Compounds" Heteroatom Chem.5 (3). 229-234 (1994)

Makoto Hojo、Naruyasu Ishibashi 和 Akira Hosomi：“杂芳基硫基甲基硅烷。羰基化合物杂芳基硫基甲基化的合成及其应用”Heteroatom Chem.5 (3)。

Makoto Hojo, Chikara Murakami, Hidenori Aihara, Ei-ichi Komori, Shinya Kohra, Yoshinori Tominaga, and Akira Hosomi: "Cross-Coupling Reaction of Pentacoordinate Alkenylsilicates with Organic Halides and Triflates Catalyzed by a Palladiium Complex" Bull.Soc

Makoto Hojo、Chikara Murakami、Hidenori Aihara、Ei-ichi Komori、Shinya Kohra、Yoshinori Tominaga 和 Akira Hosomi：“钯配合物催化的五配位链烯基硅酸盐与有机卤化物和三氟甲磺酸酯的交叉偶联反应” Bull.Soc

Makoto Hojo, Hidenori Aihara, and Akira Hosomi: "Unprecedented Reactions Mediated by Samarium : Approach to Non-Stabilized Carbonyl Ylids" J.Am.Chem.Soc.118 (in press). (1996)

Makoto Hojo、Hidenori Aihara 和 Akira Hosomi：“钐介导的前所未有的反应：非稳定羰基叶利德的方法”J.Am.Chem.Soc.118（印刷中）。

M.Hojo,H.Harada,A.Hosomi: "A Novel and Efficient Generation of Functionalized Vinylcopper Reagents and their Reactions with Electrophiles.Synthesis of β-Methylthiobutenolides" Chem.Lett.,. (3). 437-440 (1994)

M.Hojo、H.Harada、A.Hosomi：“功能化乙烯基铜试剂及其与亲电子试剂的反应。β-甲基硫代丁烯内酯的合成”Chem.Lett.，437-440 (1994)。

M.Hojo,H.Harada,C.Murakami,A.Hosomi: "Direct Generation and Reaotions of Solfur-Substituted Alylcopper Reagents by a Novel Reduction Reaction Using Organocuprute" J.Chem.Soc.,Chem.Commun.2687-2688 (1994)

M.Hojo、H.Harada、C.Murakami、A.Hosomi：“使用 Organocuprute 的新型还原反应直接生成和反应硫取代的烷基铜试剂”J.Chem.Soc.，Chem.Commun.2687-2688（