The Development of Carbon-Carbon Bond Forming Process Using Aluminum Metal as A Electron Pool

以铝金属为电子池的碳-碳键形成工艺的进展

• 批准号: 03555185
• 负责人: TORII Sigeru
• 金额: $ 10.69万
• 依托单位: OKAYAMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03555185/
• 关键词: Aluminum Metal; Bimetal Redox; Carbon-Carbon Bond Forming Reaction; Selective Functional Group Transformation; beta-Lactam; Electron Transfer Catalyst; アルミニウム; 複合金属レドックス系; 電子移動触媒系; ポリハロアルカン; ビアツール; 炭素-炭素結合形成; 特異的官能基変換; ビアリール; ベーターラクタム; 3-ヒド

Aluminum metal is an electron pool (reducing agent) which involves a lot of reactive electrons. We have demonstrated that a diverse transformation of functional groups and carbon-carbon bond forming reactions are selectively achieved by a new electron transfer process using aluminum metal as an electron source. In this project, we have investigated the following fundamental subjects in order to develop practical processes.(a) The electron transfer process from the surface of aluminum metal is highly dependent on the solvent, another redox metal, and additives. We have studied the bimetal redox system to realize the most efficient electron transfer system for the purposes.(b) Some multi metal redox systems consisting of transition metal, reducing metal, and electron pool metal have been found to achieve a variety of organic reactions involving carbon-carbon bond formation. As an example, a facile coupling reaction of alkenyl halides leading to dienes was developed.(c) The redox systems have been applied to the transformation of beta-lactam compounds and new practical synthetic processes of the antibiotics have been developed.

铝金属是一个电子池（还原剂），其中涉及大量的活性电子。我们已经证明，一个不同的功能基团和碳-碳键形成反应的转化是选择性地实现了一个新的电子转移过程中使用铝金属作为电子源。在这个项目中，我们研究了以下基本课题，以开发实用的工艺。(a)从铝金属表面的电子转移过程高度依赖于溶剂、另一种氧化还原金属和添加剂。为了实现最有效的电子转移体系，我们研究了双金属氧化还原体系。(b)由过渡金属、还原性金属和电子池金属组成的多金属氧化还原体系可以实现多种碳-碳键形成的有机反应。作为一个例子，开发了一个容易的偶联反应的烯基卤化物导致二烯。(c)将氧化还原体系应用于β-内酰胺类化合物的转化，开发了实用的抗生素合成新工艺。

项目成果

H.Tanaka, Y.Kameyama, S.Sumida, and S.Torii: "2-Substituted Penems, New Candidates for Cephalosporinase Inhibitors" Bioorganic & Medicinal Chemistry Letters. Vol.3, No.11. 2253-2254 (1993)

H.Tanaka、Y.Kameyama、S.Sumida 和 S.Torii：“2-取代青霉烯类，头孢菌素酶抑制剂的新候选者”Bioorganic

Tsutomu Inokuchi: "Indirect Electroreduction of 2-Alkyl-2-(bromomethyl)alkanones with Cobaloxime to Form 3-Alkyl-2-alkenones via 1,2-Acyl Migration" The Journal Organic Chemistry. 56. 5945-5948 (1991)

Tsutomu Inokuchi：“用钴肟间接电还原 2-烷基-2-（溴甲基）烷酮，通过 1,2-酰基迁移形成 3-烷基-2-烯酮”《有机化学》杂志。

S.Torii: "Carbonylative[2+2]Cycloaddition for the Construction of β-Lactam Skeleton with Palladium Catalyst" TETRAHEDRON LETT.34. 6553-6556 (1993)

S. Torii：“用钯催化剂构建 β-内酰胺骨架的羰基[2+2]环加成”TETRAHEDRON LETT.34 (1993)。

S.Torii, H.Okumoto and H.Yabuki: "A Facile Conversion of 2-Substituted Acrylamides to 1, 3-Disubstituted 3-Bromo-2-Azetidinones" SYNTH.COMMUN.23(4). 517-523 (1993)

S.Torii、H.Okumoto 和 H.Yabuki：“2-取代丙烯酰胺轻松转化为 1, 3-二取代 3-溴-2-氮杂环丁酮”SYNTH.COMMUN.23(4)。

Hideo Tanaka: "A Facile Synthesis of C(3)-Alkenyl Substituted Cephems through Addition-Cyclization of Allenecarboxylates derived from Penicillin^1" Tetrahedron Letters. 46. 7029-7030 (1992)

Hideo Tanaka：“通过青霉素 ^1 衍生的丙二烯羧酸盐的加成环化轻松合成 C(3)-烯基取代的头孢烯”四面体字母。