Viewed: 13:17:00 in February 27, 2020

Catalytic Regioselective γ-Methylenation of α,β-Unsaturated Aldehydes Using Formaldehyde via Vinylogous Aldol Condensation (Kutwal, Mahesh; Dev, Sachin; Appayee, Chandrakumar)
Org. Lett. 2019, 21 (8), 2509−2513.

Keywords: organocatalysis; formaldehyde; TFE

共役不飽和アルデヒドとホルムアルデヒドの反応です。市販のホルムアルデヒドにはいろいろありますが、Supporting Informationを読む限り、この論文の実験では水溶液を使っているようです。37%なのでホルマリンでしょうか。

Graphical Abstractの反応スキームを眺めると、アミン触媒と酢酸、TFE (おそらく2,2,2-トリフルオロエタノール)が使われているのがわかります。スキームを見て、光学活性のある触媒を使う必要があるのか?と思いましたが、この触媒が天然のアミノ酸由来であることを考えると、あえてラセミ体のものを用意する必要もなさそうだしこれでいいかなと。ホルムアルデヒド以外のアルデヒドの反応で生成物の光学純度を見ているようですし。あと、この触媒のトリメチルシリル基は必須のようでして、この部分が水素原子だとよろしくないのだとか。酢酸とかTFEが使われているし、反応で生成する水もあるから、触媒分子中の酸素−ケイ素結合が切断されるんじゃないかと気にしていましたが、大丈夫なのかな。

反応機構が知りたいので、読みたい論文に追加です。特にTFEの役割ですね。

論文タイトルの"regioselective"とはこういうことでしょうね。

 

Barton−Kellogg反応 [Doi 1] [Doi 2]
Borch還元的アミノ化反応 [Doi 1]
Mislow?Evans転位 [Doi 1] [Doi 2]
糖ヌクレオチドの発見と糖生合成におけるその役割についての研究 (Luis Federico Leloir)

早川電機工業がシャープに社名変更
UNIX時間
日本万国博覧会(大阪万博)開幕
日本航空機よど号ハイジャック事件
新日本製鐵(新日鐵住金)発足
ビートルズ解散
「ジムニー」発売(鈴木自動車工業=スズキ)
LSI開発(日立製作所)
日本政府が閣議で日本の呼称を「ニッポン」に統一することを決める
植村直己が北米大陸最高峰マッキンリー山に単独初登頂
米上院で大気汚染防止法案(マスキー法)が可決
三島事件
ソ連の宇宙探査機ベネラ7号が金星に着陸

 

ここの画像を使用しています。

雨でもパトロールを怠らないチャシロ。

 

Just finished the calculations: allyl ethyl ether https://t.co/N2GF3JjEqV pic.twitter.com/sePBcQItXp

— nanoniele (@nanoniele) April 24, 2019

 

　

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