Detection and Identification of Organic Compounds

Decarboxylative oxygenation of carboxylic acids with O2via a non-heme manganese catalyst

“…Carboxylic acids are one of the most important feedstocks in organic, polymer and material synthesis. 1,2 They are widely available in nature and industry, inexpensive, stable, and nontoxic in general. [3][4][5] Moreover, many carboxylic acids, such as amino acids, fatty acids and sugar acids, can be derived directly from natural resources.…”

Catalytic C–H Functionalization of Trimethylamine

“…The structure of 23 could be confirmed unambitiously by single crystal X-ray diffraction of the corresponding hydrochloride 23•HCl (Figure 3). 11 The assumption that ring strain is responsible for the stereoselective formation of E-allylamine products from the 9-membered cyclic allenes is strongly supported by the results obtained with cyclotrideca-1,2-diene and the acyclic 1,3-disubstituted allene pentadeca-7,8-diene (Table 1, entries 3 and 4). In both cases, the allenes delivered the desired branched hydroaminoalkylation products as mixtures of the corresponding E-and Z-stereoisomer in ratios of approximately 4:1 (E/Z-24 or E/Z-25).…”

“…The structure of E-7a could be confirmed unambitiously by single crystal X-ray diffraction of the corresponding hydrochloride E-7a•HCl (Figure 2). 11 In this context, it should also be mentioned that additional experiments performed with a large variety of unsymmetrically substituted diarylacetylenes always gave mixtures of both regioisomeric hydroaminoalkylation products in ratios of approximately 1:1.…”

“…Subsequently, under identical reaction conditions, a variety of additional monosubstituted alkenes could also be reacted with trimethylamine to give the corresponding hydroaminoalkylation products 11-18. Although in most cases (10)(11)(12)(13)(14)(15)(16), the products were obtained in modest to good yields (38-80 %), poor yields (14-34 %) were observed in a few examples (17,18), mainly due to poor conversion of the alkene starting materials. However, the good yield of 68 % observed in the case of triisopropylsilylether 12 proves that the reaction also tolerates the presence of protected oxygen functionalities.…”

“…In this case, best results were obtained with a reduced catalyst loading of only 5 mol% TiBn4 and LH1 at 60 °C. 10 The relative configuration of 29 was elucidated by single crystal X-ray diffraction of the corresponding hydrochloride 29•HCl (Figure 4), 11 and it was found that 29 has the expected cis-orientation of the dimethylaminomethyl substituent and the cyclopropane hydrogen atoms. This finding is in good agreement with closely related DFT-calculations 16 which have already shown that hydroaminoalkylation of a corresponding methylenecyclopropane with secondary amines can only occur from its convex side.…”