A Synthetic Approach to 15-D_2c-Isoprostane Ethyl Ester

The preparation of ketone 10 is described. Oxidation of 10 to the sulfoxide followed by sigmatropic rearrangement gave not the expected 15-D2c-isoprostane ethyl ester (4), but the trans diastereomer 11. A 13C NMR method for establishment of the relative configuration of the cyclopentane rings of the isoprostanes and prostaglandins is also reported

Synthesis of 2,3-Dinor-5,6-dihydro-15F_2t-isoprostane

A concise synthesis of the 15-F2t-isoprostane urinary metabolite 2, a potential marker for systemic oxidative stress, is described. This synthesis confirmed the structure of this important product of human metabolism. The key transformation is the rhodium-mediated diastereoselective cyclization of diazo ketone 4, followed by cyclopropane ring opening with thiophenol and Lewis acid. Material prepared by the synthesis outlined here will be used to develop an antibody-based assay for clinically quantifying systemic oxidative stress

A Synthetic Approach to 15-D_2c-Isoprostane Ethyl Ester

The preparation of ketone 10 is described. Oxidation of 10 to the sulfoxide followed by sigmatropic rearrangement gave not the expected 15-D2c-isoprostane ethyl ester (4), but the trans diastereomer 11. A 13C NMR method for establishment of the relative configuration of the cyclopentane rings of the isoprostanes and prostaglandins is also reported

5-F_2t-Isoprostane, A Human Hormone?

Syntheses of the four enantiomerically pure diastereomers of 5-F2t-isoprostane (5−8) are described. The key step is the lipase-catalyzed chemo-enzymatic resolution of the racemic diol 40 to give the mono-acetates 41 and 42. The enantiomerically pure diastereomers of 5-F2t-isoprostane (5) may be human hormones

Rhodium-Catalyzed Reformatsky-Type Reaction

A novel Reformatsky-type reaction was developed using RhCl(PPh3)3 and diethylzinc. Inter- and intramolecular Reformatsky-type reactions were achieved efficiently under mild reaction conditions to give β-hydroxy esters

2,5-Dialkyl Cyclohexenones by Fe(CO)₅-Mediated Carbonylation of Alkenyl Cyclopropanes: Functional Group Compatibility

The preparation of alkenyl cyclopropanes 1 with a variety of common organic functionalities is reported. These substrates were subjected to the Fe(CO)5-mediated carbonylation process under a CO atmosphere, leading to the formation of 2,5-disubstituted cyclohexenones 2, important intermediates for target-directed synthesis

2,5-Dialkyl Cyclohexenones by Fe(CO)₅-Mediated Carbonylation of Alkenyl Cyclopropanes: Functional Group Compatibility

The preparation of alkenyl cyclopropanes 1 with a variety of common organic functionalities is reported. These substrates were subjected to the Fe(CO)5-mediated carbonylation process under a CO atmosphere, leading to the formation of 2,5-disubstituted cyclohexenones 2, important intermediates for target-directed synthesis

Enantiomerically Pure Cyclohexenones by Fe-Mediated Carbonylation of Alkenyl Cyclopropanes

Enantiomerically Pure Cyclohexenones by Fe-Mediated Carbonylation of Alkenyl Cyclopropane