The power of two metals: A Pd/Cu catalyst system mediates the in situ formation of acyl nucleophiles by decarboxylation of readily accessible and stable salts of α‐oxocarboxylic acids and their cross‐coupling with aryl or heteroaryl bromides to give ketones. The reaction may be used in the presence of many functional groups and provides good yields.

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In the presence of catalytic amounts of magnetite nanopowder, mixtures of aromatic and aliphatic carboxylic acids are converted selectively into the corresponding aryl alkyl ketones. As byproducts, only carbon dioxide and water are released. This catalytic cross-ketonisation allows the regioselective acylation of aromatic systems and, thus, represents a sustainable alternative to FriedelCrafts acylations.Keywords: aryl alkyl ketones; catalysis; cross-ketonisation; decarboxylation; iron Aryl alkyl ketones are among the most important synthons in the industrial manufacture of commodities, [1] fine chemicals, and pharmaceuticals.[2] Simple derivatives, at early stages of the chemical value creation chain, are synthesised almost exclusively via FriedelCrafts acylation of arenes, because the low cost of this reaction is unrivalled to date.[3] However, two main issues are associated with this approach. Its low regioselectivity leads to the co-manufacture of large amounts of isomeric by-products, and the use of acyl chlorides as starting materials activated with superstoichiometric amounts of salt mediators (e.g., AlCl 3 ) is responsible for the formation of enormous quantities of salt waste.Regioselective and less waste-intensive acylations, e.g., cross-couplings [4] of sensitive arylmetal reagents with either preformed [5] or in situ-generated [6] carboxylic acid derivatives are widely used to access highervalue synthetic intermediates. However, their high cost precludes their application in the manufacture of base chemicals. This is also the case for alternative approaches, such as Heck-type reactions, [7] or the Pdcatalysed decarboxylative cross-coupling of a-oxocarboxylate salts with aryl halides.[8] Thus, a clear need remained for a broadly applicable, regioselective and waste-minimised aryl alkyl ketone synthesis starting from simple, inexpensive, and widely available chemicals.As a solution to this long-standing problem, we envisioned a catalytic process in which an aromatic and an aliphatic carboxylic acid are cross-coupled under release of CO 2 and water, to selectively give the aryl alkyl ketone (Scheme 1). In such a decarboxylative cross-ketonisation, the carboxylate groups would predefine the position of bond formation, potentially allowing a selective synthesis of any desired regioisomer. If mediated by catalytic amounts of an inexpensive metal with high selectivity for hetero-over homocoupling, the overall process would be advantageous both from economical and ecological standpoints.The decarboxylative homoketonisation of aliphatic carboxylic acids is an established strategy for the preparation of symmetrical dialkyl ketones or cyclic alkanones.[9] State-of-the-art protocols involve gasphase transformations at temperatures above 350 8C at solid catalysts, for example, CaO, ZnO, MgO, [10] TiO 2 , [11] ZrO 2 , [12] MnO, [13] Fe 2 O 3 , [14] or rare earth metal oxides [15] on SiO 2 -, Al 2 O 3 -, or pumice-based supports. However, if equimolar mixtures of aromatic and aliphatic carboxylic acids ar...

The aim of this study was to evaluate the diagnostic value of monitoring CD64 antigen upregulation on polymorphonuclear neutrophils (PMN) for the identification of infectious complications in the postoperative course of solid organ transplanted patients. Twenty-five kidney, 13 liver, and four pancreas-kidney transplanted patients were included. Beginning with preoperative values up to postoperative values after 3 months for each patient, the PMN CD64 Index, HLA-DR on monocytes, NKp44 1 NK and NK/T cells, CXCR31 NK cells, CXCR3 1 T helper cells, CXCR3 1 NK/T cells, and CD4/ CD8 ratio were measured by flow cytometry. Subsequently they were correlated with confirmed postoperative complications. Measuring the PMN CD64 Index reached a sensitivity of 89% and a specificity of 65% in the detection of infectious complications. Concerning this matter, it was a significantly better marker than all other included parameters except CXCR31 NK/T cells. In contrast, according to our results the PMN CD64 Index has no diagnostic relevance in detection of rejections. The combination of included parameters showed no improved diagnostic value. Due to its high sensitivity and specificity for infectious complications CD64 on PMN could be proven a very good indicator in evaluating suspected infectious complications in the postoperative course of transplanted patients. ' 2011 International Society for Advancement of Cytometry