Zirconium‐ and Silicon‐Containing Intermediates with Three Fused Rings in a Zirconocene‐Mediated Intermolecular Coupling Reaction

Abstract

Scheme 3. A proposed reaction mechanism involving one siliconatom-tethered diyne and three organonitriles. Scheme 4. Further applications of intermediate 6 a. Angewandte Chemie 7365

Reactions of Isocyanides with Metal Carbyne Complexes: Isolation and Characterization of Metallacyclopropenimine Intermediates

“…Isocyanides have been recognized as versatile building blocks in a variety of metal-mediated and metal-catalyzed organic syntheses, enabling efficient transformation to elaborate organic structures . Most examples of metal-mediated and/or metal-catalyzed reactions of isocyanide species involve the insertion of an isocyanide molecule into a metal–element bond . C–C couplings involving coordinated isocyanide ligands have long been known, , which are similar to those well-established reductive C–C couplings involving isoelectronic carbonyls .…”

Unusual Nitrile–Nitrile and Nitrile–Alkyne Coupling of FcCN and FcCCCN

“…The reaction of zirconocene compounds with diynes and different nitriles (for example, PhÀCN, tBuÀCN) was already described in detail by Xi and co-workers. [5] The chosen nitrile influences significantly the outcome of the reaction with Group 4 metallocenes, thus indicating a broad reaction pattern.…”

Efficient One‐Pot Synthesis of N‐Containing Heterocycles by Multicomponent Coupling of Silicon‐Tethered Diynes, Nitriles, and Isocyanides through Intramolecular Cyclization of IminoacylZr Intermediates

“…When bis(alkynyl)silane 1 a , i PrCN, and t BuNC were used, tetrasubstituted 5‐azaindole 6 a was formed in 63 % isolated yield, with only the isocyanide carbon atom being integrated into the product (Table 1, entry 1). The newly formed carbon–hydrogen bond was found to originate from the hydrolysis process 15b. Changing the isocyanide from t BuNC to both aliphatic CyNC and aromatic 2,6‐dimethylphenyl isocyanide led to the same 5‐azaindole 6 a as the main product in 65 and 54 % yields, respectively (Table 1, entries 2 and 3).…”

“…A peak at m / z =73 that could be assigned to the relative molecule weight of t BuNH 2 was found. The residue was washed with diethyl ether several times until it turned in to a pale solid and was further characterized by elemental analysis to be 7 15b…”

“…The extract was dried over anhydrous MgSO 4 and the solvent was evaporated in vacuo to give a yellow solid, which was purified by using an SiO 2 column with petroleum ether, diethyl ether, and triethylamine (100:10:1) as the eluent to give product 6 d . The characterization data of product 6 a has been published in our previous communication 15b…”