Viewed: 09:15:34 in December 9, 2019

Allyl-Nickel Catalysis Enables Carbonyl Dehydrogenation and Oxidative Cycloalkenylation of Ketones (Huang, David; Szewczyk, Suzanne M.; Zhang, Pengpeng; Newhouse, Timothy R.)
J. Am. Chem. Soc. 2019, 141 (14), 2298−2301.

Keywords: C−H bond activation; Ni; dme; THF

ニッケル触媒による、脱水素を伴う炭素−炭素結合形成反応について報告しています。Graphical Abstractにはこの研究の肝の部分である単純な概念図が描かれていますが、論文に記載の反応はもっと複雑なようで、環状の化合物からさらなる反応、具体的には二重結合の移動が起こるケースもあるようです。

反応の様相が大雑把にわかりそうなのが下の反応スキームです。Graphical Abstractにあるアリルニッケル種は、臭化ニッケルとリン酸のアリルエステル、そして、亜鉛化合物から発生させているようです。TMPが具体的に何を指すのかは、本文を読まないとわからないようです。そして、これも実際に本文を読まないとわかりませんが、亜鉛化合物の使用量から、sp³炭素−水素結合がニッケル触媒により活性化されるのではない、単純な酸−塩基反応である可能性があります。

生成物ですが、Supporting Informationから、5員環の形成が有利であること、ジアステレオ選択的な炭素−炭素結合形成は可能であること、出発化合物の炭素−炭素二重結合の幾何異性は保持できないことが伺えます。

反応の全体の様相や機構を知りたいので、読みたい論文に追加しました。Supporting Informationには基質合成に関する膨大な記述がありますので、本文に記載の反応例も多数・多様にあるのだと思っています。

実験方法の、マイクロ波合成用の容器に試薬を入れて油浴で加熱するというのが面白い。

 

Albright−Goldman酸化 [Doi 1]
Conia−Ene反応 [Doi 1]
Kochi反応 [Doi 1]
Tsuji−Trost反応 [Doi 1] [Doi 2]
Tsuji−Wilkinson脱カルボニル化 [Doi 1]
有機合成化学に対する顕著な貢献
(Robert Burns Woodward)
「ジャルパック」発売(日本航空)
「オロナミンCドリンク」発売(大塚製薬)
富士山レーダー観測開始
「イリオモテヤマネコ」新種として鑑定・命名
人類初の宇宙遊泳
「サンオイル」発売(資生堂)
荒川放水路が荒川本流に
チリで大地震発生
初の国産旅客機YS-11が就航
東京電力が電気料金の銀行口座振替制を開始
「小川宏ショー」放送開始(フジテレビ)
日本サッカーリーグ開幕
日韓基本条約
名神高速道路が全線開通
「アイスノン」発売(鎌田商会=白元アース)
日医工設立
松代群発地震
共同石油(ジャパンエナジー)設立
「エメロンシャンプー」発売(ライオン油脂=ライオン)
池谷・関彗星発見
みどりの窓口開設
「テンダーリンス」発売(花王石鹸=花王)
ブルーボーイ事件
日本最初のカラーテレビアニメ「ジャングル大帝」放送開始(フジテレビ)
F1メキシコGPでホンダが初優勝
「11PM」「おはよう!こどもショー」放送開始(日本テレビ)
プロ野球第1回ドラフト会議
名阪国道が開通

 

ここの画像を使用しています。

まだ冬毛のたぬき。この時季にうちの庭に来るのは珍しい。

 

Just finished the calculations: 1-chloro-3,3,4,4-tetramethyl-2,5-dioxasilacyclopentane (PinSiHCl) https://t.co/voNtP34BgW @nanoniele pic.twitter.com/QNH57k6fkW

— nanoniele (@nanoniele) April 17, 2019

 

　

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