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This work describes the employment of discrete “AgCF3” complexes as efficient transmetalating agents to PdIIto surmount overlooked challenges related to the transmetalation step in Pd- catalyzed trifluoromethylation processes. We report the participation of a unique silver ate (Cs)[Ag(CF3)2] complex, under stoichiometric and catalytic conditions, in the unprecedented one-pot formation of PhCF3 using PhI as starting material. Moreover, we show that the transmetalation step, which is often ignored in these transformations, can also determine the success or failure of the coupling process.

Póster presentado en BIOTRANS 2015, celebrado del 26 al 30 de julio de 2015 en Viena (Austria), Intramolecular stereoselective carboligations are important reactions in organic synthetic chemistry essential for the access of natural occurring compounds and analogues. Besides the chemical methodologies, a plethora of intramolecular C-C bond forming reactions exists in different metabolic pathways of living organism catalyzed by highly evolved enzymes. Examples of carboligases such as of aldolases or ThDP depending enzymes performing asymmetric intramolecular aldol reactions with synthetic substrates are scarce in the literature. In this work, we endeavored to investigate on the intramolecular C-C bond formation via benzoin reaction catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I (BAL). We investigate BAL-catalyzed intramolecular benzoin reaction on benzaldehyde moieties substrates connected with a spacer derivative via ether linkage (i.e. 2,2'- (1), 3,3’ (2) and 4,4’ (3)-(n-alkane-1,n-diylbis(oxy))dibenzaldehyde derivatives). The reaction performance comparing the intra and inter benzoin reaction with substrates 1-3 as well as their analogues with symmetric and unsymmetrical aromatic substitutions was investigated. The results obtained of substrate conversion, stereochemical outcome of the enzymatic reactions and molecular models that intended to explain the reactivity of the different substrates will be reported.

Table S1. One-way ANOVAs of identified metabolites in leaf organ and epispheric. Table S2 One-way ANOVAs of identified metabolites in flowers organ and epispheric. Table S3 One-way ANOVAs of identified metabolites in in leaf organ in different antibiotic treatment within the plants receiving control levels of water in leaf. Table S4 One-way ANOVAs of identified metabolites in identified in leaf epispheric in different antibiotic treatment within the plants receiving control levels of water in leaf. Table S5 One-way ANOVAs of identified metabolites in in flowers organ in different antibiotic treatment within the plants receiving control levels of water in leaf. Table S6 One-way ANOVAs of identified metabolites in in flowers epispheric in different antibiotic treatment within the plants receiving control levels of water in leaf. Table S7 Abbreviation, family and the real name of the metabolites detected. (PDF 3529 kb)

Table S1. One-way ANOVAs of identified metabolites in leaf organ and epispheric. Table S2 One-way ANOVAs of identified metabolites in flowers organ and epispheric. Table S3 One-way ANOVAs of identified metabolites in in leaf organ in different antibiotic treatment within the plants receiving control levels of water in leaf. Table S4 One-way ANOVAs of identified metabolites in identified in leaf epispheric in different antibiotic treatment within the plants receiving control levels of water in leaf. Table S5 One-way ANOVAs of identified metabolites in in flowers organ in different antibiotic treatment within the plants receiving control levels of water in leaf. Table S6 One-way ANOVAs of identified metabolites in in flowers epispheric in different antibiotic treatment within the plants receiving control levels of water in leaf. Table S7 Abbreviation, family and the real name of the metabolites detected. (PDF 3529 kb)