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Connor S. MacNeil Lauren N. Mendelsohn Hongyu Zhong Tyler P. Pabst Paul J. Chirik 《Angewandte Chemie (International ed. in English)》2020,59(23):8912-8916
Intermediates relevant to cobalt‐catalyzed alkene hydroformylation have been isolated and evaluated in fundamental organometallic transformations relevant to aldehyde formation. The 18‐electron (R,R)‐(iPrDuPhos)Co(CO)2H has been structurally characterized, and it promotes exclusive hydrogenation of styrene in the presence of 50 bar of H2/CO gas (1:1) at 100 °C. Deuterium‐labeling studies established reversible 2,1‐insertion of styrene into the Co?D bond of (R,R)‐(iPrDuPhos)Co(CO)2D. Whereas rapid β‐hydrogen elimination from cobalt alkyls occurred under an N2 atmosphere, alkylation of (R,R)‐(iPrDuPhos)Co(CO)2Cl in the presence of CO enabled the interception of (R,R)‐(iPrDuPhos)Co(CO)2C(O)CH2CH2Ph, which upon hydrogenolysis under 4 atm H2 produced the corresponding aldehyde and cobalt hydride, demonstrating the feasibility of elementary steps in hydroformylation. Both the hydride and chloride derivatives, (X=H?, Cl?), underwent exchange with free 13CO. Under reduced pressure, (R,R)‐(iPrDuPhos)Co(CO)2Cl underwent CO dissociation to form (R,R)‐(iPrDuPhos)Co(CO)Cl. 相似文献
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Dr. Martin Pabst Prof. Renato Zenobi Prof. Petra S. Dittrich 《Angewandte Chemie (International ed. in English)》2015,54(5):1671-1675
We present a novel and straightforward screening method to detect protein phosphorylations in complex protein mixtures. A proteolytic digest is separated by a conventional nanoscale liquid chromatography (nano‐LC) separation and the eluate is immediately compartmentalized into microdroplets, which are spotted on a microarray MALDI plate. Subsequently, the enzyme alkaline phosphatase is applied to every second microarray spot to remove the phosphate groups from phosphorylated peptides, which results in a mass shift of n×?80 Da. The MALDI‐MS scan of the microarray is then evaluated by a software algorithm to automatically identify the phosphorylated peptides by exploiting the characteristic chromatographic peak profile induced by the phosphatase treatment. This screening method does not require extensive MS/MS experiments or peak list evaluation and can be easily extended to other enzymatic or chemical reactions. 相似文献
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L. W. Winkler E. Ekman A. Samyschlayewa W. Zimmermann K. Bodendorf N. Prileshajew L. Kofler F. Krämer P. HOrkheimer J. Reilly N. Noonan P. J. Drumm W. Peyer H. Iffinger S. Kroll W. J. Blackie J. F. Clevenger M. L. Pabst A. R. Bliss jun R. W. Morrison und E. O. Prather jun 《Fresenius' Journal of Analytical Chemistry》1935,102(3-4):141-146
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