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以己内酰胺铑[Rh2(cap)4]为催化剂,叔丁基过氧化氢(TBHP)为氧化剂,在二异丙基乙胺(DIPEA)中,甲醇被氧化成甲醛后与1,3-二羰基化合物(1a~1j)经缩合反应合成了一系列双-1,3-二羰基化合物(2a~2j,其中2i和2j为新化合物),其结构经1H NMR,13C NMR和HR-ESI-MS表征。在最佳反应条件[1a 1.0 mmol,Rh2(cap)41.0 mol%,TBHP 3.0 mmol,DIPEA 1.2 mmol,于室温反应2 h]下,双-苯甲酰乙酸甲酯(2a)的收率83%。首次报道Rh2(cap)4对甲醇的催化氧化反应,而且可以用1对2进行捕捉。
In the presence of rhodium [Rh2 (cap) 4] as catalyst and t-butyl hydroperoxide (TBHP) as oxidant in diisopropylethylamine (DIPEA), methanol was oxidized to formaldehyde and reacted with 1,3-dicarbonyl A series of bis-1,3-dicarbonyl compounds (2a ~ 2j, where 2i and 2j are novel compounds) were synthesized by condensation reaction of compounds (1a ~ 1j). The structures were confirmed by 1H NMR, 13C NMR and HR-ESI-MS Characterization. The yield of methyl bis-benzoylacetate (2a) was 83% under the optimal reaction conditions [1a 1.0 mmol, 41.0 mol% Rh2 (cap), 3.0 mmol TBHP, 1.2 mmol DIPEA, reaction at room temperature for 2 h] . For the first time, the catalytic oxidation of Rh2 (cap) 4 to methanol was reported and it was possible to capture it with one pair of two.