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The Metalation of ( tert ‐Butyldimethylsilyl)(2‐pyridylmethyl)amine with Dimethylzinc and Subsequent Zinc‐Mediated Carbon−Carbon Coupling Reaction
Author(s) -
Westerhausen Matthias,
Bollwein Tobias,
Makropoulos Nikolaos,
Rotter Thomas M.,
Habereder Tassilo,
Suter Max,
Nöth Heinrich
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200103)2001:3<851::aid-ejic851>3.0.co;2-z
Subject(s) - chemistry , dimethylzinc , metalation , zinc , medicinal chemistry , amine gas treating , inorganic chemistry , amide , organic chemistry
The lithiation of 2‐(aminomethyl)pyridine and the subsequent reaction with ClSiMe 2 t Bu yields ( tert ‐butyldimethylsilyl)(2‐pyridylmethyl)amine ( 1 ). The metalation of 1 with dimethylzinc gives colorless dimeric methylzinc 2‐pyridylmethyl( tert ‐butyldimethylsilyl)amide ( 2 ), which crystallizes in the triclinic space group P 1¯. The solvent‐free thermal decomposition of 2 at 150 °C leads to the evolution of methane, the precipitation of zinc metal and the formation of amine 1 , bis(methylzinc)—1,2‐dipyridyl‐1,2‐bis( tert ‐butyldimethylsilylamido)ethane ( 3 ), and bis[( tert ‐butyldimethylsilyl)(2‐pyridylmethyl)amido]zinc ( 4 ). Compound 3 can be obtained in good yield by reacting 2 with dimethylzinc at elevated temperatures in toluene. During this reaction, zinc metal precipitates and methane is evolved. The C−C coupling product 3 crystallizes in the tetragonal space group I 4 1 cd . The lithiation of 1 and the subsequent metathesis reaction with anhydrous ZnCl 2 yields complex 4 almost quantitatively.