Viewed: 18:36:58 in March 30, 2020

Dehydrogenative Coupling of Benzylic and Aldehydic C–H Bonds (Kawasaki, Tairin; Ishida, Naoki; Murakami, Masahiro)
J. Am. Chem. Soc. 2020, 142 (7), 3366−3370.

Keywords: Ir; Ni; dtbbpy; TBAB; TEMPO; 読みたい論文シリーズ; 有機化学; ブログ

Ni/Ir触媒による、ベンジル炭素と脂肪族アルデヒドのカルボニル炭素の脱水素カップリングに関する論文のようです。青色光の照射下で進行します。

イリジウム触媒はこんな構造。

この反応、脱水素カップリングですので、反応により脱離する2つの水素原子を酸化剤で補足される、水素分子が生じるのどちらかであるはずで、その辺りどうなっているのかなと思ったのが、読みたい論文に追加に至る「入口」でした。確かにGraphical Abstractからは水素分子の生成とありますが、実際には確認がなされてないにも関わらずH₂と書いてある他の著者の論文も過去に見られ、ここはしっかり見とかないととSupporting Informationを読みました。確かにきっちりと書かれています、よかった。

…という不安が解消されたとか私のどうでもいい話はさておき、この反応、捕捉実験からラジカル機構で進んでいることは容易に想像でき、どのようなラジカルサイクルを想定しているのか、興味が引かれます。ラジカル機構であるためか、反応の適用範囲も納得のいくもので、芳香環上の置換基とベンジルラジカル発生の容易さの関係、アルデヒドのチョイス、などなど、本文を読む前から頷けるものがあります。

有機ラジカル反応であることが容易に想像できる一方、有機ラジカル発生に至るIr/Ni触媒の挙動については知識不足のためか本文を読まなければどうにもなりません。使用しているニッケル錯体のアニオン種が何かしていそうなことはSupporting Informationからわかりますが…。

 

☆ラジカル (radical)

不対電子を持つ原子や分子。不対電子を持つイオンの場合はラジカルイオンとも。
日本語では遊離基。
不対電子を持つので、磁性を潜在的に持つ。

 

Just finished the calculations: phenyl trifluoroacetate https://t.co/06tklCiw7N pic.twitter.com/3xthm5Tqbc

— nanoniele (@nanoniele) February 20, 2020

 

　

 

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