Abstract
A novel tetrameric copper(I) complex containing tert-butyldiallylphosphine ligands, [CuCl{tBu-P(CH2CH=CH2)2}]4 (2), has been synthesized and characterized by structural and spectroscopic methods. X-ray diffraction analysis showed that 2has a cubane-like solid structure of formula [CuCl{κ1(P)-tBu-P(CH2CH=CH2)2}]4. In solution, a dynamic behavior generated by the cubane⇄chair isomerization was detected by variable temperature NMR analysis. DFT calculations have been performed to explain the observed dynamic equilibrium in solution. The use of copper(I) complex 2 as catalyst for the synthesis of propargylamines via A3-coupling reactions has been tested. Complex 2 is capable of promoting A3-coupling reactions of both aromatic and aliphatic aldehydes with cyclic secondary amines and phenylacetylene. The reaction proceeds under mild condition and absence of solvent.
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