Practical Chemoselective Acylation: Organocatalytic Chemodivergent Esterification and Amidation of Amino Alcohols with N-Carbonylimidazoles.

Chemoselective transformations are a cornerstone of efficient organic synthesis; however, achieving this goal for even simple transformations, such as acylation reactions, is often a challenge. We report that N-carbonylimidazoles enable catalytic chemodivergent aniline or alcohol acylation in the presence of pyridinium ions or 1,8-diazabicyclo[5.4.

InChI version 1.06: now more than 99.99% reliable.

The software for the IUPAC Chemical Identifier, InChI, is extraordinarily reliable. It has been tested on large databases around the world, and has proved itself to be an essential tool in the handling and integration of large chemical databases. InChI version 1.

One-pot Unsymmetrical Ketone Synthesis Employing a Pyrrole-Bearing Formal Carbonyl Dication Linchpin Reagent.

A one-pot procedure for the synthesis of unsymmetrical ketones utilizing a pyrrole-bearing carbonyl linchpin reagent (carbonyl linchpin N,O-dimethylhydroxylamine pyrrole; CLAmP) is reported. In contrast to other carbonyl dielectrophile equivalents, CLAmP enables the synthesis of ketones from a variety of organolithium and Grignard reagents. The electrophilic nature of CLAmP enables the addition of less reactive as well as thermally unstable nucleophiles.

InChI, the IUPAC International Chemical Identifier.

This paper documents the design, layout and algorithms of the IUPAC International Chemical Identifier, InChI.

Protic-solvent-mediated cycloisomerization of quinoline and isoquinoline propargylic alcohols: syntheses of (±)-3-demethoxyerythratidinone and (±)-cocculidine.

Putting the "benz" in indolizinones: A cycloisomerization approach to benz[g]indolizinones and benz[e]indolizinones provides the first general route to these unique azacycles (see example). The utility of the benzindolizinone products was demonstrated by the application of this method to the total synthesis of the Erythrina alkaloids 3-demethoxyerythratidinone and cocculidine.

Enantioselective cyclization of enamide-ynes and application to the synthesis of the kopsifoline core.

We report the palladium-catalyzed enantioselective cyclization of 1,6-enamidynes to form spirocyclic ring systems. We applied this methodology to the concise synthesis of the skeletal core of the kopsifoline alkaloids.

InChI - the worldwide chemical structure identifier standard.

Since its public introduction in 2005 the IUPAC InChI chemical structure identifier standard has become the international, worldwide standard for defined chemical structures. This article will describe the extensive use and dissemination of the InChI and InChIKey structure representations by and for the world-wide chemistry community, the chemical information community, and major publishers and disseminators of chemical and related scientific offerings in manuscripts and databases.

Utility of the short double-balloon enteroscope to perform pancreaticobiliary interventions in patients with surgically altered anatomy in a US multicenter study.

Objective: Double-balloon enteroscopy-assisted endoscopic retrograde cholangiopancreaticography (DBE-ERCP) is an effective method for interventions in the pancreaticobiliary system in the post-surgical patient. However, use of currently available endoscopic accessories during this procedure is limited due of the length of the conventional instrument (200 cm). The aim of this study was to explore the utility of the short DBE (152 cm) for the management of pancreaticobiliary disorders in patients with surgically altered anatomies.

Dual Brønsted acid/nucleophilic activation of carbonylimidazole derivatives.

Carbonylimidazole derivatives have been found to be highly active acylation reagents for esterification and amidation in the presence of pyridinium salts. These reactions are thought to involve both Brønsted acid and nucleophilic catalysis. This mode of activation has been applied to the synthesis of difficult to access oxazolidinones, as well as esters and amides.

Small bowel cancers diagnosed by device-assisted enteroscopy at a U.S. referral center: a five-year experience.

Background: Primary malignant neoplasms of the small bowel comprise only 1-3% of all gastrointestinal malignancies. Small bowel cancers pose a significant diagnostic challenge. The recent development of video capsule endoscopy (VCE) and device-assisted enteroscopy (DAE) have greatly facilitated evaluation of the small bowel.

Current status of advanced gastrointestinal endoscopy training fellowships in the United States.

Rapid growth in the field of advanced gastrointestinal endoscopy has led to an increase in specialized therapeutic endoscopy fellowships. The cornerstones of these programs are training in endoscopic retrograde cholangiopancreatography (ERCP) and endoscopic ultrasound. These procedures are more complex and challenging to master than routine colonoscopy and upper endoscopy, and in the case of ERCP, higher risk.

Chemoselective esterification and amidation of carboxylic acids with imidazole carbamates and ureas.

Imidazole carbamates and ureas were found to be chemoselective esterification and amidation reagents. A wide variety of carboxylic acids were converted to their ester or amide analogues by a simple synthetic procedure in high yields.

Open-label, sham-controlled trial of an endoscopic duodenojejunal bypass liner for preoperative weight loss in bariatric surgery candidates.

Background: The duodenojejunal bypass liner (DJBL) (EndoBarrier Gastrointestinal Liner) is an endoscopically placed and removable intestinal liner that creates a duodenojejunal bypass resulting in weight loss and improvement in type 2 diabetes mellitus.

Objective: Weight loss before bariatric surgery to decrease perioperative complications.

Design: Prospective, randomized, sham-controlled trial.

Double-balloon enteroscopy in the elderly: safety, findings, and diagnostic and therapeutic success.

Background: Double-balloon enteroscopy (DBE) is an important tool in the evaluation and management of small-bowel disease. Limited data are available on the safety, findings, and outcomes of DBE in elderly patients.

Objective: To determine the safety and efficacy of DBE in elderly patients.

Lithogenesis and bile metabolism.

Gallstone disease exacts a considerable financial and social burden worldwide leading to frequent physician visits and hospitalizations. Based on their composition, gallstones are categorized as cholesterol, black pigment, and brown pigment, with each category having a unique structural, epidemiologic, and risk factor profile. Cholesterol crystal formation requires the presence of one or more of the following: (a) cholesterol supersaturation, (b) accelerated nucleation, or (c) gallbladder hypomotility/bile stasis.

Rapid access to pyrazolo[3,4-c]pyridines via alkyne annulation: limitations of steric control in nickel-catalyzed alkyne insertions.

Polyfunctionalized pyrazolo[3,4-c]pyridines were readily prepared by the annulation of alkynes with tert-butyl 4-iodopyrazolocarboximines. The reaction was found to be catalyzed by both NiBr2(PPh3)2/Zn or PdCl2(PhCN)2 to yield complex heterocycles in good to moderate yields. Annulation using nickel catalysis was found to be regio-random, implying that steric control in nickel-catalyzed alkyne insertion has limitations based on the character of the Ni-C bond in the pre-insertion complex.

The changing role of a publisher and the publisher of the future.

The manner in which the slow, but inevitable, change in the way scientists will communicate in the future is presented. Examples from past and recent history show how change, while difficult for many, does and will occur in spite of large barriers, primarily from the existing power structure of the organization in charge and control of scientific publishing and database distribution. Those forward thinking and acting publishers who understand these changes will be able to develop new products which will both help the scientist in his/her work and be a viable economic business model for such companies to prosper in the future.

p38 MAP kinase inhibitors. Part 6: 2-arylpyridazin-3-ones as templates for inhibitor design.

p38 inhibitors based on 3,4-dihydropyrido[4,3-d]pyrimidazin-2-one template were synthesized and their SAR explored. Benchmark compounds 30, 35, and 36 were found to be potent against the enzyme. Crystal structure of p38 in complex with 30 indicated a key pi-stacking interaction with the pendant tyrosine residue-35 in the glycine-rich loop.

1,3-diketones from acid chlorides and ketones: a rapid and general one-pot synthesis of pyrazoles.

[reaction: see text] 1,3-Diketones were synthesized directly from ketones and acid chlorides and were then converted in situ into pyrazoles by the addition of hydrazine. This method is extremely fast, general, and chemoselective, allowing for the synthesis of previously inaccessible pyrazoles and synthetically demanding pyrazole-containing fused rings.

Managing industrial risk--having a tested and proven system to prevent and assess risk.

Some relatively easy techniques exist to improve the risk picture/profile to aid in preventing losses. Today with the advent of computer system resources, focusing on specific aspects of risk through systematic scoring and comparison, the risk analysis can be relatively easy to achieve. Techniques like these demonstrate how working experience and common sense can be combined mathematically into a flexible risk management tool or risk model for analyzing risk.

Microscopic colitis. Identical clinical presentations of subtypes create diagnostic challenges.

The diagnosis of microscopic colitis should be considered in patients presenting with chronic watery diarrhea, especially middle-aged and elderly women. Diagnosis is established by colonoscopic biopsies showing histologic changes in the setting of endoscopically normal mucosa. Although the etiology of microscopic colitis remains unknown, a wide variety of effective medical treatments is available.