Photocatalytic Asymmetric Acyl Radical Truce Smiles Rearrangement for the Synthesis of Enantioenriched α-Aryl Amides.

The radical Truce-Smiles rearrangement is a straightforward strategy for incorporating aryl groups into organic molecules for which asymmetric processes remains rare. By employing a readily available and non-expensive chiral auxiliary, we developed a highly efficient asymmetric photocatalytic acyl and alkyl radical Truce-Smiles rearrangement of α-substituted acrylamides using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom-transfer photocatalyst, along with aldehydes or C-H containing precursors. The rearranged products exhibited excellent diastereoselectivities (7:1 to >98:2 d.r.) and chiral auxiliary was easily removed. Mechanistic studies allowed understanding the transformation in which density functional theory (DFT) calculations provided insights into the stereochemistry-determining step.

TBADT-Mediated Photocatalytic Stereoselective Radical Alkylation of Chiral N-Sulfinyl Imines: Towards Efficient Synthesis of Diverse Chiral Amines.

Herein we describe a sustainable and efficient photocatalytic method for the stereoselective radical alkylation of chiral sulfinyl imines. By employing readily available non-prefunctionalized radical precursors and the cost-effective TBADT as a direct HAT photocatalyst, we successfully obtain diverse chiral amines with high yields and excellent diastereoselectivity under mild conditions. This method provides an efficient approach for accessing a diverse array of medicinally relevant compounds, including both natural and synthetic α-amino acids, aryl ethyl amines, and other structural motifs commonly found in approved pharmaceuticals and natural product.

Metal-free photocatalytic cross-electrophile coupling enables C1 homologation and alkylation of carboxylic acids with aldehydes.

In contemporary drug discovery, enhancing the sp3-hybridized character of molecular structures is paramount, necessitating innovative synthetic methods. Herein, we introduce a deoxygenative cross-electrophile coupling technique that pairs easily accessible carboxylic acid-derived redox-active esters with aldehyde sulfonyl hydrazones, employing Eosin Y as an organophotocatalyst under visible light irradiation. This approach serves as a versatile, metal-free C(sp3)-C(sp3) cross-coupling platform. We demonstrate its synthetic value as a safer, broadly applicable C1 homologation of carboxylic acids, offering an alternative to the traditional Arndt-Eistert reaction. Additionally, our method provides direct access to cyclic and acyclic ß-arylethylamines using diverse aldehyde-derived sulfonyl hydrazones. Notably, the methodology proves to be compatible with the late-stage functionalization of peptides on solid-phase, streamlining the modification of intricate peptides without the need for exhaustive de-novo synthesis.

Primary malignant melanoma of the bowel diagnosed following a bowel intussusception in an adult patient. A case report and review of the literatureport.

AIM: Primary small bowel melanoma is a very rare clinical entity with a paucity of publications in literature. Most cases of gastrointestinal melanomas are metastatic lesions arising generally from primary lesion of the skin, eyes, or anus. We present a case of a small bowel intussusception with primary malignant melanoma as lead point and a gluteal melanoma metastasis after four years free from disease. CASE REPORT: A 77-year-old female has come to our attention with signs and symptoms of intestinal occlusion. She was subjected to a computerized tomography (CT) of the abdomen and pelvis that revealed small bowel intussusception caused by intestinal polypoid lesion. She was treated with a bowel resection. The histological exam has shown the presence of an amelanocytic malignant melanoma. The examination of skin, eyes, esophagus, colon and anus, a tot al body contrast- enhanced CT and a bone scintigraphy were negative for primary melanoma. So, the final diagnosis was primary melanoma of the ileum. After four-years disease-free survival, the patient came back to our attention for a gluteal melanoma metastasis, that was surgically removed. Afterwards she started immunotherapy, that is still ongoing. DISCUSSION AND CONCLUSION: The diagnosis and the treatment of primary intestinal melanoma is a challenging due to the lack of scientific indications. Our case shows how an early diagnosis, although accidental, can offer a good survival free from disease. Moreover, a careful follow-up of our patients allows us to promptly identify neoplasm recurrence or distant metastasis that can be treated with surgery and systematic therapy. KEY WORDS: Intussusception, Primary bowel melanoma.

Syntheses of new chiral chimeric photo-organocatalysts.

A new family of chiral chimeric photo-organocatalysts derived from phosphoric acid were synthesized and their spectroscopic and electrochemical properties were investigated. Then, the ability of these photo-activable molecules to catalyse an asymmetric tandem electrophilic ß-amination of enecarbamates was evaluated.

Branch Duct - IPMN and PanIN, in IgG4-Autoimmune pancreatitis: A case report.

The presence of pancreatic lesions in patients with autoimmune pancreatitis requires histological diagnosis (percutaneous or endoscopic biopsy) to exclude malignancy. A nonspecific histology after endoscopic or percutaneous biopsy of a pancreatic lesion may require surgical excision and definite histology.

Galileo, measurement of the velocity of light, and the reaction times.

According to the commonly accepted view, Galileo Galilei devised in 1638 an experiment that seemed able to show that the velocity of light is finite. An analysis of archival material shows that two decades later members of the Florence scientific society Accademia del Cimento followed Galileo guidelines by actually attempting to measure the velocity of light and suggesting improvements. This analysis also reveals a fundamental difference between Galileo's and Florence academy's methodologies and that Galileo's experiment was, in some respects, a pioneering work affecting also the history of the psychology of perception.