Total Synthesis of Bipenicilisorin and Assignment of the Absolute Configuration.

The first total synthesis of bipenicilisorin (1) isolated from Penicillium chrysogenum SCSIO 41001 via its monomer natural product, penicilisorin (2), was achieved. Penicilisorin was synthesized in four steps from a o-bromobenzaldehyde derivative via the Pd-catalyzed one-pot fluorocarbonylation/lactonization/ß-elimination cascade reaction. Iodination of penicilisorin gave 7-iodopenicilisorin which was dimerized by Pd-catalyzed homodimerization to provide (±)-bipenicilisorin. The unknown absolute configuration of naturally occurring (+)-bipenicilisorin was examined by optical resolution of the (±)-synthetic bipenicilisorin and a comparison of experimental and theoretical electronic circular dichroism (ECD) spectra. These results support the absolute configuration of the natural product to be Sa. A cytotoxic activity test of (+)-and (-)-bipenicilisorin using A549 cells revealed that (+)-1 has a lower IC50 value than (-)-1.

First Total Syntheses of Beauvericin A and allo-Beauvericin A.

The first total syntheses of beauvericin A and allo-beauvericin A were achieved. N-Methyl-l-phenylalanine, (2R)-hydroxylvaleric acid, and (2R,3S)- or (2R,3R)-2-hydroxy-2-methylpentanoic acid were linked and cyclized to form the target natural products. The structure of synthetic beauvericin A was confirmed by X-ray crystallographic analysis. NMR data of the synthetic beauvericins were identical with those of the reported natural products. These results secure the structures of natural products, as originally proposed in the isolation studies.

Totally implantable venous access port via the femoral vein in a femoral port position with CT-venography.

BACKGROUND AND PURPOSE: We aimed to determine the success rate and any complications using a percutaneous approach to the femoral vein (FV) for placement of a totally implantable access port (TIVAP), with a preoperative assessment of the femoral and iliac veins using computed tomography-venography (CT-V). METHODS: A prospective study of 72 patients was conducted where placement of a TIVAP was attempted via the right FV, with the port placed in the anterior thigh, when subclavian vein or jugular vein access was contraindicated. Preoperative assessment of the femoral venous plexus was performed with CT-V in 72 patients. RESULTS: CT-V success was achieved in 72 of 72 patients (100%). The average distance between the inguinal ligament and the saphenofeomral (FV-GSV) junction was 42.8 ± 12.9 mm. The FV approach had a 97% successful cannulation rate. Two patients had a thrombosis in either the femoral vein or the great saphenous vein. One procedural complication (1.4%) and one initial complication (1.4%) occurred. Late complications occurred in four patients (5.7%). CONCLUSIONS: The percutaneous FV approach with CT-V guidance is an option for patients with multiple central venous cannulations, as well as those with bilateral breast cancer, or those undergoing hemodialysis. J. Surg. Oncol. 2016;114:1024-1028. © 2016 Wiley Periodicals, Inc.