· Copper(I) Bis(trimethylsilyl)amide
· (MW 223.93)
(reagent for the conversion of aryl and vinyl iodides into the corresponding amines)
Alternate Name: copper(I) hexamethyldisilazide.
Physical Data: colorless crystals, subl. 180 °C/0.2 mmHg.1
Preparative Methods: prepared in situ from Lithium Hexamethyldisilazide and Copper(I) Iodide.
Handling, Storage, and Precautions: moisture and oxygen sensitive.
The title reagent couples with aryl iodides in boiling pyridine (18 h) to give the corresponding silyl-protected primary aromatic amine, ArN(SiMe3)2 (1), in approximately 50% yield.2 Methanolysis of (1) quantitatively liberates the free amine, ArNH2. Aryl bromides also couple with (Me3Si)2NLi to give (1), but higher temperatures (160 °C in quinoline, 18 h) are necessary. 1-Iodo-6-alkylcycloheptatrienes can be converted into their 1-amino counterparts using this reagent.3 Finally, this reagent deoxygenates carbon dioxide in the presence of added ligand to produce a copper(I) isocyanate complex which can be further transformed into an alkyl isocyanate by treatment with an alkyl iodide.4
- 1. Burger, H.; Wannagat, U. M 1964, 95, 1099.
- 2. King, F. D.; Walton, D. R. M. CC 1974, 256.
- 3. Okazaki, R.; O-oka, M.; Tokitoh, N.; Shishido, Y.; Inamoto, N. AG(E) 1981, 20, 799.
- 4. Tsuda, T.; Washita, H.; Saegusa, T. CC 1977, 468.
David R. M. Walton
University of Sussex, Brighton, UK
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