[読みたい論文] アルカリ土類金属触媒による水素移動反応

Viewed: 15:02:39 in December 16, 2019

Posted: March 21, 2019

[Angew. Chem. Int. Ed. 2019, 58 (13), 4248−4253] Alkene Transfer Hydrogenation with Alkaline-Earth Metal Catalysts (Bauer, Heiko; Thum, Katharina; Alonso, Mercedes; Fischer, Christian; Harder, Sjoerd)

Keywords: Ca; Ba; Sr; hmdsH; 1,4-cyclohexadiene; benzene

hmds配位子がくっついたアルカリ土類金属触媒による水素移動反応。アルケンが水素化されて、1,4-シクロヘキサジエンがベンゼンになるようです。π共役の力は偉大です。なおアルケンが存在しない場合には1,4-シクロヘキサジエンの不均化が起こりシクロヘキシンとベンゼンが生成する模様。


この反応ですが、金属触媒と1,4-シクロヘキサジエンと反応してhmds配位子が一旦離れないことには反応が進まないのではと思うのです。金属−水素結合が形成しないとアルケンへの水素移動が起きないのではないでしょうか。つまり、単純な酸塩基反応ではなく、σ-結合メタセシスの機構が反応の鍵になっているのでは…

…とか思いながらSupporting informationには酸塩基反応とσ-結合メタセシスの両方の機構を想定した計算がなされたと思われるデータがあります。どちらの機構が支配的なのかは論文本体を読まないといけないようです。金属触媒(の成れの果て)と1,4-シクロヘキサジエン(の成れの果て)とアルケン全てが関与した協奏的な水素移動が起きているような構造もあります。反応のモニタリングデータから速度式を決めるような実験は、Supporting informationからは確認できませんでした。

というわけで、読みたい論文に追加です。ところでマグネシウムでの検討はしてないんですかね?

この記事を書いた人
「牧岡ふうふ堂」オーナー。博士(工学)。
酒都圏在住。
某地方の国立系工業大学でアシスタントをしていました。 専門は有機反応・金属錯体(主に希土類)・π共役系。
twitterアカウントは@makiokafufudo(お仕事用)、@ymakioka(個人用)です。

 

1946年はこんな年

人名反応など
Gallagher&minusHollander分解Jones酸化 [Doi 1]
ノーベル化学賞
酵素とウイルスタンパク質の結晶化
(James Batcheller Sumner, John Howard Northrop, Wendell Meredith Stanley)
できごと
日本国憲法公布
医師国家試験制度実施
文部省が当用漢字を発表
文部省が公民館設置を市町村に通達
文部省が六三三四教育制度を発表
厚生省が日本脳炎を法定伝染病に指定
経済同友会創立
経済団体連合会設立
日本商工会議所設立
日本製薬株式会社設立
フランス銀行が国有化
国際連合総会第1回開催
国際連盟が解散を決議
日本新聞協会設立
神社本庁設立
昭和南海地震
手塚治虫「マアチャンの日記帳」連載開始
秋葉原電気街が露店として開業
のど自慢素人音楽会(NHKのど自慢)放送開始
西部水産速報(みなと新聞・山口新聞)発刊
日刊スポーツ創刊

 

きょうのどうぶつ

ここの画像を使用しています。

黒い猫の個体識別は難しい。クロ2号か?

 

あわせてどうぞ

SOHOのすすめ記事一覧 2019年
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読みたい論文シリーズ − 2019年1Q
読みたいけと読んでいない論文を、構造式を描きながら紹介します(2019年1〜3月)。

 

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