The ground and low-lying excited states of the 5-dehydro-meta-xylylene and 2-dehydro-meta-xylylene triradicals, as well as their derivatives are characterized by the equation-of-motion spin-flip coupled-cluster method with single and double substitutions. The effect of substituents in the C2, C4, and C6 positions on electronic states ordering is investigated. In the 5-dehydro-meta-xylylene trir...

A new protocol for the aromatization of tetrahydrocarbazoles has been achieved using a catalytic amount of iodine, giving high yields. The role of iodine in the aromatization has been explained by DFT, and its wide scope is extended to the total synthesis of glycozoline and murrayafoline A. This method has proven to be tolerant of a broad range of functional groups.

A synthesis of moracin M using Appel dehydration a biomimetic inspired endoperoxide and subsequent late stage aromatization, is described. key 1,3-diene, obtained from base-free Suzuki-Miyaura coupling, can undergo oxidation to its endoperoxide, followed by under conditions aromatization give benzofuran, with deprotection then providing in only 4-steps. Alternatively, this 1,3‑diene synthetic r...

OBJECTIVES We tested the hypothesis that insulin resistance, per se, contributes to increased platelet activation in obesity, independently of underlying inflammation. BACKGROUND Obesity, insulin resistance, and atherosclerosis are closely linked phenomena associated with low-grade inflammation. Obesity is associated with persistent platelet activation in otherwise healthy women. METHODS We...

A platinum-catalyzed reaction involving new aromatization/1,3-carbonyl shift cascade of 2-epoxy-1-(methoxyalk-2-ynyl)benzenes is reported. This skeletal rearrangement is mechanistically significant because it involves a remarkable 1,3-carbonyl shift to complete the aromatization and to regenerate the catalyst.

OBJECTIVE We aimed at investigating the relationship between Helicobacter pylori infection and in vivo lipid peroxidation and platelet activation, as reflected by urinary 8-iso-prostaglandin (PG)F(2alpha) and 11-dehydro-thromboxane (TX)B2, respectively, in otherwise healthy dyspeptic subjects. METHODS AND RESULTS We measured urinary 8-iso-PGF2alpha and 11-dehydro-TXB2 excretion in 40 dyspepti...

Dehydro-L-ascorbic acid is usually found in plant tissues in low concentrations and is always associated with ascorbic acid in much higher concentrations. One of the most reliable and direct methods for its estimation is that originally proposed by Roe & Kuether (1943) which is based on the formation of a 2:4-dinitrophenylosazone. Many plant tissues, however, contain so little dehydro-L-ascorbi...

BACKGROUND Increased platelet thromboxane (TX)A2 production has been described in type IIa hypercholesterolemia. To verify the relevance of these capacity-related measurements to the actual rate of TXA2 biosynthesis in vivo, we studied the urinary excretion of its major enzymatic metabolites in 46 patients with type IIa hypercholesterolemia and 20 age-matched controls. METHODS AND RESULTS Uri...

[3H8]Thromboxane B2 was biosynthesized and infused into an unanesthetized monkey. Several urinary metabolites were isolated and their structures elucidated using gas chromatography-mass spectrometry. In addition to the major urinary metabolite, dinor-thromboxane B2, a series of metabolites resulting from dehydrogenetion of the alcohol group at C-11 were identified: 11-dehydro-thromboxane B2, 11...

Stable enols were synthesized from the reaction of (1Z,3Z)-1,4-dilithio-1,3-dienes with acid chlorides and structurally characterized by single-crystal X-ray analysis. These stable enols were formed by a novel de-aromatization/Michael addition/re-aromatization domino process.