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Gold-catalyzed [4+3]-Annulations of Benzopyriliums with Vinyldiazo Carbonyls to Form Bicyclic Heptatriene Rings with Skeletal Rearrangement
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Gold-catalyzed [4+3]-Annulations of Benzopyriliums with Vinyldiazo Carbonyls to Form Bicyclic Heptatriene Rings with Skeletal Rearrangement

Antony Sekar Kulandai RajRai-Shung Liu
Advanced Synthesis and Catalysis
2020

摘要

2-Alkynylbenzaldehyde Annulations Benzopyriliums Rearrangement Vinyldiazo carbonyls Catalysis Organic Chemistry
We report gold catalyzed [4+3]-annulations between benzopyriliums and 3-alkyl-2-diazo-3-vinyl carbonyls, yielding 7H-benzo[7]annulene products efficiently. Notably, the carbon skeletons of resulting 7H-benzo[7]annulenes are structurally rearranged, accompanied by migrations of their alkyl and ketone motifs. Apart from applicable substrates over a wide scope, these annulatios are applicable to pyriliums and 3-alkyl-2-diazo-3-vinyl esters to increase their reaction significance. We postulate a mechanism involving an initial [4+2]-cycloaddition between benzopyriliums and 3-alkyl-2-diazo-3-vinyl carbonyl species, followed by formation of gold carbenes to induce a ring expansion and group migrations.

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