Alkoxy-1,3,5-triazapentadien(e/ato) copper(II) complexes: template formation and applications for the preparation of pyrimidines and as catalysts for oxidation of alcohols to carbonyl products

Template combination of copper acetate (Cu(AcO)₂?H₂O) with sodium dicyanamide (NaN(C≡N)₂, 2 equiv) or cyanoguanidine (N≡CNHC(=NH)NH₂, 2 equiv) and an alcohol ROH (used also as solvent) leads to the neutral copper(II)–(2,4‐alkoxy‐1,3,5‐triazapentadienato) complexes Cu{NH?C(OR)NC(OR)?NH}₂] (R=Me ( 1 ), Et ( 2 ), nPr ( 3 ), iPr ( 4 ), CH₂CH₂OCH₃ ( 5 )) or cationic copper(II)–(2‐alkoxy‐4‐amino‐1,3,5‐triazapentadiene) complexes Cu{NH?C(OR)NHC(NH₂)?NH}₂](AcO)₂ (R=Me ( 6 ), Et ( 7 ), nPr ( 8 ), nBu ( 9 ), CH₂CH₂OCH₃ ( 10 )), respectively. Several intermediates of this reaction were isolated and a pathway was proposed. The deprotonation of 6 – 10 with NaOH allows their transformation to the corresponding neutral triazapentadienates Cu{NH?C(OR)NC(NH₂)?NH}₂] 11 – 15 . Reaction of 11 , 12 or 15 with acetyl acetone (MeC(?O)CH₂C(?O)Me) leads to liberation of the corresponding pyrimidines NC(Me)CHC(Me)NC NHC(?NH)OR, whereas the same treatment of the cationic complexes 6 , 7 or 10 allows the corresponding metal‐free triazapentadiene salts {NH₂C(OR)?NC(NH₂)?NH₂}(OAc) to be isolated. The alkoxy‐1,3,5‐triazapentadiene/ato copper(II) complexes have been applied as efficient catalysts for the TEMPO radical‐mediated mild aerobic oxidation of alcohols to the corresponding aldehydes (molar yields of aldehydes of up to 100 % with >99 % selectivity) and for the solvent‐free microwave‐assisted synthesis of ketones from secondary alcohols with tert‐butylhydroperoxide as oxidant (yields of up to 97 %, turnover numbers of up to 485 and turnover frequencies of up to 1170 h^?1).