85924-42-1Relevant articles and documents
Synthesis and field test of a pheromone analog of chilecomadia valdiviana
Herrera, Heidy,Barros-Parada, Wilson,Fernanda Flores,Fuentes-Contreras, Eduardo,Bergmann, Jan
, p. 4019 - 4022 (2018)
The main pheromone component of Chilecomadia valdiviana has recently been reported to be (7Z,10Z)-7,10-hexadecadienal. The synthesis of a structural analog, (5Z,8Z)-5,8-tetradecadienyl formate is reported. The pheromone analog was not attractive to male C
Synthesis of isotopically labeled arachidonic acids to probe the reaction mechanism of prostaglandin H synthase
Peng, Sheng,Okeley, Nicole M.,Tsai, Ah-Lim,Wu, Gang,Kulmacz, Richard J.,Van der Donk, Wilfred A.
, p. 10785 - 10796 (2007/10/03)
Prostaglandin H synthase (PGHS) catalyzes the conversion of arachidonic acid to prostaglandin G2 in the cyclooxygenase reaction. The first step of the mechanism has been proposed to involve abstraction of the pro-S hydrogen atom from C13 to generate a pentadienyl radical spanning C11-C15. We report here the synthesis of six site-specifically deuterated arachidonic acids to investigate the structure of the radical intermediate. The preparation of these compounds was achieved using a divergent scheme that involved one advanced intermediate for all targets. The synthetic design introduced the label late in the routes and allowed the utilization of common synthetic intermediates in the preparation of various targets. Both 13(R)- and 13(S)-deuterium-labeled arachidonic acids were synthesized in high enantiomeric purity as deduced from soybean lipoxygenase assays and mass spectrometric analysis of the resulting enzymatic products. Each synthetic compound was reacted under anaerobic conditions with the wide singlet tyrosyl radical of PGHS-2 to generate a radical intermediate that was analyzed by EPR. Deuterium substitution at positions 11, 13(S), and 15 resulted in the loss of one hyperfine interaction, indicating that the protons at these positions interact with the unpaired electron. Simulation of the spectra was achieved with one set of parameters that are consistent with the assignment of a pentadienyl radical. Use of 16-[2H2]-arachidonic acid indicated that only one of the protons at C16 gives rise to a strong hyperfine interaction. The findings are discussed in the context of two proposed mechanisms for the cyclooxygenase reaction.
The first total synthesis of (-)-lipstatin
Pommier,Pons,Kocienski
, p. 7334 - 7339 (2007/10/03)
A key step in the first total synthesis of the potent pancreatic lipase inhibitor (-)-lipstatin (1) is a diastereoselective Lewis acid-promoted [2 + 2] cycloaddition reaction between n-hexyl(trimethylsilyl)ketene (4) and (R)-(-)-(Z,Z)-3-[(tert-butyldimethylsilyl)oxy]-5,8-tetradecadienal (3), which is prepared from dimethyl (S)-(-)-malate.
