An efficient triphenylphosphine oxide (Ph3PO) catalyzed amidation and esterification reaction for rapid synthesis of a series of dipeptides, amides and esters under mild condition is described. This reaction is applicable to challenging couplings of hindered carboxylic acid with low nucleophilic amine or alcohol, giving products in good yields (67-90%) without any racemization. This system employs highly reactive intermediate Ph3PCl2 as activator of carboxylate, in a catalytic manner, and drive the reaction to complete in short reaction time (less than 10 min). It has the advantages of good functional group tolerance, broad substrate scope and good atom-economy. A 100 mmol scale reaction with good yield shed light on its potential for industrial application. A plausible mechanism is proposed based on 31 P NMR monitor of reaction process.
Supporting InformationComplete experimental procedures and characterization of new products; NMR spectra and HPLC chromatograms (PDF)
Enantioselective synthesis of α-amino esters have been achieved through the Petasis borono-Mannich multicomponent reaction using ( R)-BINOL-derived catalysts with stable heteroaryl and alkenyl trifluoroborate salts under mild conditions. The reaction provides direct access to optically active α-amino esters with moderate to good yields and enantioselectivities.
An efficient triphenylphosphine oxide (Ph3PO) catalyzed amidation and esterification reaction for rapid synthesis of a series of dipeptides, amides and esters under mild condition is described. This reaction is applicable to challenging couplings of hindered carboxylic acid with low nucleophilic amine or alcohol, giving products in good yields (67-90%) without any racemization. This system employs highly reactive intermediate Ph3PCl2 as activator of carboxylate, in a catalytic manner, and drive the reac-tion to complete in short reaction time (less than 10 min). It has the advantages of good functional group tolerance, broad sub-strate scope and good atom-economy. A 100 mmol scale reaction with good yield shed light on its potential for industrial ap-plication. A plausible mechanism is proposed based on 31P NMR monitor of reaction process.
An efficient triphenylphosphine oxide (Ph3PO) catalyzed amidation and esterification reaction for rapid synthesis of a series of dipeptides, amides and esters under mild condition is described. This reaction is applicable to challenging couplings of hindered carboxylic acid with low nucleophilic amine or alcohol, giving products in good yields (67-90%) without any racemization. This system employs highly reactive intermediate Ph3PCl2 as activator of carboxylate, in a catalytic manner, and drive the reaction to complete in short reaction time (less than 10 min). It has the advantages of good functional group tolerance, broad substrate scope and good atom-economy. A 100 mmol scale reaction with good yield shed light on its potential for industrial application. A plausible mechanism is proposed based on 31 P NMR monitor of reaction process.
Supporting InformationComplete experimental procedures and characterization of new products; NMR spectra and HPLC chromatograms (PDF)
Metal phosphate are important catalyst and materials in synthesis chemistry. Herein, we describe the synthesis and characterization of phosphate‐catecholate chelated Nd(III), Zr(IV) and Al(III) chlorides (2‐5). These species are achieved via ethyl chloride elimination reaction of oxophosphoranes with corresponding metal chlorides. The product 2‐5 represent a new serial of monometallic and bimetallic phosphate‐catecholate chelated metal complexes stabilized by both P‐O and catecholate‐O donors. These findings pave the way for future explorations of such species in catalysis.
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