The neoclerodane diterpene salvinorin A (1) was isolated in 1982 from the rare mint SalVia diVinorum, indigenous to Oaxaca, Mexico. 1 Recent efforts established salvinorin A as a potent and selective κ opioid receptor agonist, the only non-alkaloid psychoactive substance, and the most potent naturally occurring hallucinogen. 2 As a result of its therapeutic potential, renewed isolation efforts have discovered a number of related salvinorin congeners, 3 and a number of analogues of 1 have been prepared by semisynthesis to probe the pharmacophore and mode of binding. 4 This communication describes the first synthesis of this natural product.Construction of the tricyclic salvinorin core is predicated on the proposed transannular 5 Michael reaction cascade 6 of bisenone macrocycle 3 (Scheme 1). Conformational analysis 7 of 3 leads to a prediction wherein the resident stereocenters at C 2 , C 4 , and C 12 should mutually reinforce the desired stereochemical course of the reaction. This plan permits the convergent assembly of vinyl iodide Scheme 5. Transannular Cyclization Analysis
In broccoli, sulforaphane forms when the glucosinolate glucoraphanin is hydrolyzed by the endogenous plant thiohydrolase myrosinase. A myrosinase cofactor directs hydrolysis away from the formation of bioactive sulforaphane and toward an inactive product, sulforaphane nitrile. The cofactor is more heat sensitive than myrosinase, presenting an opportunity to preferentially direct hydrolysis toward sulforaphane formation through regulation of thermal processing. Four broccoli cultivars were microwave heated, boiled, or steamed for various lengths of time. Production of nitrile during hydrolysis of unheated broccoli varied among cultivars from 91 to 52% of hydrolysis products (Pinnacle > Marathon > Patriot > Brigadier). Boiling and microwave heating caused an initial loss of nitrile, with a concomitant increase in sulforaphane, followed by loss of sulforaphane, all within 1 min. In contrast, steaming enhanced sulforaphane yield between 1.0 and 3.0 min in all but Brigadier. These data are proof of concept that steaming for 1.0-3.0 min provides less nitrile and more sulforaphane yield from a broccoli meal.
SUMMARYWe report a case of a giant pancreatic pseudocyst in a 65-year-old man presenting with abdominal pain, loss of appetite and abdominal distension. CT scans demonstrated a giant pancreatic pseudocyst measuring 25.7 cm ×15.3 cm×10.9 cm anteroposteriorly, with significant compression of surrounding organs. An open cystogastrostomy was performed through a midline incision, and 3 L of fluid was drained from the giant pseudocyst. Recovery has been uneventful.
BACKGROUND
The X-ray structures of hydrocarbons that crystallize on special positions, and thus possess one or more crystallographic symmetry elements, were compared to DFT-calculated structures of the same hydrocarbons in the gas phase. Of the roughly 400 structures examined, at least 9% crystallize with a site symmetry that is not a subgroup of the symmetry of the ideal, lowest-energy, gas-phase structure. Thus, the crystal conformations of these molecules are very different from their ground-state conformations in the absence of packing forces, not merely modest distortions of their ideal structures. Most of the anomalous structures in our sample are higher-energy, inversion-symmetric conformations of molecules that possess chiral or polar ground-state conformations, suggesting that the well-known propensity of crystals to form with centers of inversion frequently leads molecules to adopt anomalous conformations in the solid state.
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