Alkyne Insertion into P–C(sp2) Bonds as a Route to Fused Phospholes: Transition-Metal-Like Reactivity at Phosphorus
| Autor: | Brian T. Sterenberg, Shrikant Nilewar, Arumugam Jayaraman |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
chemistry.chemical_classification
Annulation 010405 organic chemistry Aryl Organic Chemistry Regioselectivity Alkyne 010402 general chemistry Ring (chemistry) 01 natural sciences Medicinal chemistry 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound Electrophilic substitution chemistry Insertion reaction Reactivity (chemistry) Physical and Theoretical Chemistry |
| Zdroj: | Organometallics. 37:4699-4710 |
| ISSN: | 1520-6041 0276-7333 |
| Popis: | While alkyne insertion into metal–carbon(sp2) bonds is common in transition metal chemistry, direct alkyne insertions into E–C(sp2) bonds are very rare in main group chemistry. Herein, we report a direct alkyne insertion reaction into the P–C(aryl) bonds of tungsten-coordinated phenyl-aryl phosphenium ions, which lead to phenyl-vinyl phosphenium ions. The insertion reaction is followed by electrophilic substitution of the phosphenium ion onto the aryl group, leading to a net annulation reaction and formation of arene and heteroarene-fused phospholes. The regioselectivity of the products and computational chemistry have been used to elucidate the insertion-electrophilic substitution mechanism. This methodology has been used to synthesize known benzophosphole and phospholo[3,2-b]thiophene and new phospholo[3,2-b]pyrrole, phospholo[2,3-b]pyrrole, and phospholo[2,3-b]indole ring systems. |
| Databáze: | OpenAIRE |
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