Cascade C-H Activation and Two C-C Bond Forming in Reaction of Azalutetacyclopentadiene with 2-Methylbenzonitriles.

Autor: Chai Z; Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications & Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China., Lv ZJ; Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications & Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China., Liu W; Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications & Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China., Yang J; Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications & Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China., Wei J; Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications & Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China., Zhang WX; Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications & Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Sep 19; Vol. 30 (53), pp. e202402311. Date of Electronic Publication: 2024 Sep 06.
DOI: 10.1002/chem.202402311
Abstrakt: Azametallacyclopentadienes are an important class of metallacycles as the key intermediates in metal-promoted or catalyzed carbon-carbon coupling reaction of nitriles and alkynes. Rare-earth azametallacyclopentadienes have shown various reactivity toward nitriles, depending on the substituents of nitriles. The reaction of azalutetacyclopentadienes toward 2-methylbenzonitriles has been investigated in this work, which selectively affords the fused 7-5-6-membered azalutetacycles as products. Computational studies reveal that the reaction of azalutetacyclopentadienes toward 2-methylbenzonitriles selectively initiates with the remote activation of the benzylic C-H bond by the Lu-N bond, followed by the intramolecular nucleophilic attack from the deprotonated benzylic carbon to form a C-C bond. Subsequently, the high ring strain promoted the generation of the uncoordinated carbanion dissociated from the lutetium center, which then undergoes intramolecular nucleophilic attack toward C=N triple bond to give the final product containing fused 7-5-6-membered azalutetacycle. This work not only achieves highly selective three-step cascade reaction to form a unique class of rare-earth metallacycle, but also provides a new idea for the transformation of unsaturated substrates with C-H bonds that can be activated.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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