96150-84-4Relevant academic research and scientific papers
Organocatalytic one-pot oxidative cleavage of terminal diols to dehomologated carboxylic acids
Shibuya, Masatoshi,Doi, Ryusuke,Shibuta, Takuro,Uesugi, Shun-Ichiro,Iwabuchi, Yoshiharu
supporting information, p. 5006 - 5009 (2013/01/15)
The organocatalytic one-pot oxidative cleavage of terminal 1,2-diols to one-carbon-unit-shorter carboxylic acids is described. The combination of 1-Me-AZADO (cat.), NaOCl (cat.), and NaClO2 caused smooth one-pot oxidative cleavage under mild conditions. A broad range of substrates including carbohydrates and N-protected amino diols were converted without epimerization. Terminal triols and tetraols respectively underwent cleavage of their C-2 and C-3 moieties to afford their corresponding two- and three-carbon-unit-shorter carboxylic acids.
Experimental and computational investigation of the uncatalyzed rearrangement and elimination reactions of isochorismate
DeClue, Michael S.,Baldridge, Kim K.,Kast, Peter,Hilvert, Donald
, p. 2043 - 2051 (2007/10/03)
The versatile biosynthetic intermediate isochorismate decomposes in aqueous buffer by two competitive pathways, one leading to isoprephenate by a facile Claisen rearrangement and the other to salicylate via elimination of the enolpyruvyl side chain. Computation suggests that both processes are concerted but asynchronous pericyclic reactions, with considerable C-O cleavage in the transition state but relatively little C-C bond formation (rearrangement) or hydrogen atom transfer to the enolpyruvyl side chain (elimination). Kinetic experiments show that rearrangement is roughly 8-times more favorable than elimination. Moreover, transfer of the C2 hydrogen atom to C9 was verified by monitoring the decomposition of [2-2H]isochorismate, which was prepared chemoenzymatically from labeled shikimate, by 2H NMR spectroscopy and observing the appearance of [3-2H]pyruvate. Finally, the isotope effects obtained with the C2 deuterated substrate are in good agreement with calculations assuming pericyclic reaction mechanisms. These results provide a benchmark for mechanistic investigations of isochorismate mutase and isochorismate pyruvate lyase, the enzymes that respectively catalyze the rearrangement and elimination reactions in plants and bacteria.
Biosynthesis of ω-cyclohexyl fatty acids in Alicyclobacillus acidocaldarius: The stereochemistry of the initial 1,4-conjugate elimination
Handa, Sandeep,Floss, Heinz G.
, p. 153 - 154 (2007/10/03)
The 1,4-conjugate elimination of H2O from shikimic acid 3, the initial step in the biosynthesis of ω-cyclohexyl fatty acids by the bacterium Alicyclobacillus acidocaldarius, has been shown to occur with an overall anti stereochemistry via loss
A Synthetic Approach to the Squalestatins and Zaragozic Acids: Introduction of the C5 Stereocentre via an Ester-Enolate Claisen Rearrangement. The X-Ray Crystal Structure of an Intermediate
Gable, Robert W.,McVinish, Leasa M.,Rizzacasa, Mark A.
, p. 1537 - 1544 (2007/10/02)
In an overall plan to synthesize the anti-cholesterol agents the squalestatins and zaragozic acids, introduction of the C5 stereochemistry was achieved via an Ireland-Claisen rearrangement of the allyl ester (7) followed by methylation, which gives the es
The Convergent Synthesis of Polyether Ionophore Antibiotics: The Synthesis of the Monensin Bis(tetrahydrofuran) via the Claisen Rearrangement of an Ester Enolate with a β-Leaving Group
Ireland, Robert E.,Norbeck, Daniel W.
, p. 3279 - 3285 (2007/10/02)
The monensin bis(tetrahydrofuran) 25, a versatile intermediate for the synthesis of polyether ionophore antibiotics, is prepared from D-xylose and D-mannose.In the key step, in situ silylation of an ester enolate with a β-leaving group allows the tetrahyd
