[読みたい論文] ハロゲン化アリールのハロゲン/サマリウム交換: ハロゲン/マグネシウム交換よりも100万倍近く速い

Viewed: 03:12:44 in December 11, 2019

Posted: March 14, 2019

[Angew. Chem. Int. Ed. 2019, 58 (12), 4046−4050] The Halogen−Samarium Exchange Reaction: Synthetic Applications and Kinetics (Anthore-Dalion, Lucile; Benischke, Andreas D.; Wei, Baosheng; Berionni, Guillaume; Knochel, Paul)

Keywords: Sm; Mg; Zn; rare earth

有機亜鉛の大家、Prof. Paul Knochelらのグループによる研究です。


nBu2Sm·4LiClやnBuSm·5LiClによるハロゲン化アリール類のハロゲン/サマリウム交換反応についての報告のようです。ハロゲン/サマリウム交換反応により発生したアリールサマリウム種はアルデヒド、ケトン、イミン、アミド等と反応しするのですが、教科書的な有機マグネシウムの反応との差異がどんなものなのか、気になるところです。

Supporting informationにはシクロプロパン環をもつケトンとの反応例が報告されていますが、有機マグネシウムだとシクロプロパン環の開裂が起こるんだっけな、忘れた。それともラジカル反応ではないことを示したかったのか。この辺りのことは、論文本体を読まないとわからないですね。

そしてこのハロゲン/サマリウム交換反応、有機マグネシウムと臭化化アリールの臭素/マグネシウム交換よりも臭素/サマリウム交換の方が100万倍近く速いとこの論文では報告していて、その理由が炭素−金属結合のイオン性や金属の電気陰性度と関連があると要旨には記述してあります。ちなみにWikipediaによるとサマリウムとマグネシウムとリチウムの電気陰性度はそれぞれ1.17と1.31と0.98です。

個人的な興味もあり、読みたい論文に追加です。リチウムフリーの系で検討した方がいいんじゃないかなとは思いましたが、難しいか。Graphical abstractにこの反応載せるんだったら、4-tert-ブチルシクロヘキサンの反応も検討すればよかったのに。


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。

 

1941年はこんな年

人名反応など
Nazarov環化
ノーベル化学賞
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できごと
米国で世界初となるテレビ放送を開始
北大西洋ポルトガル沖で地震(M8.2)
台湾全島で地震
日本海洋学会創立
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那須のアルパカちゃん。

 

あわせてどうぞ

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