Mass spectrometry aldol reactions

Trost et al. [11] reported another impressive example of bimetallic catalysts in which a Zn-Zn homobimetallic complex (17, Scheme 7) serves as an effective catalyst for direct aldol reactions [11-13]. The proposed structure of the catalyst was verified by mass spectrometry and the best ratio of Et2Zn and the ligand. The chemical yield was moderate in the reaction of methyl ketones (1) (Scheme 7, top) [11,12], but a highly atom-economic system was achieved when a-hydroxylated ketones (10) were used as a substrate (Scheme 7, bottom) [13]. Excellent diastereo- and enantioselectivity were obtained under mild conditions. In contrast to the case of Shibasaki s heteropolymetallic catalyst, syn-1,2-diols (syn-11) were obtained as the major diastereomers. 

Besides alkoxides, acetylacetonates are also used as the starting materials for the synthesis of oxides. Titania (anatase) is obtained by decomposition of titanium oxyacetylacetonate (TiO(acac)2) in toluene at 300°C. Similarly solvothermal treatment of Fe(lll) acetylacetonate in toluene yields microcrystalline magnetite. One of the drawbacks of the use of acetylacetonate may be formation of various high boiling point organic by-products via aldol-type condensation of the acetylacetone. Actually more than 50 compounds are detected by gas chromatography-mass spectrometry (GC-MS) analysis of the supernatant of the reaction, some of which are phenolic compounds and are hardly removed from the oxide particles by washing with acetone. ... 

Fig. 7. Main reactions in the aldol condensation of acetone. The different products could reliably be detected in the products stream of an 80 channel reactor filled with different zeolite eatalysts by quantitative mass spectrometry (reproduced with kind permission from [35]).

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