Concise and Practical Asymmetric Synthesis of a Challenging Atropisomeric HIV Integrase Inhibitor.

A practical and efficient synthesis of a complex chiral atropisomeric HIV integrase inhibitor has been accomplished. The combination of a copper-catalyzed acylation along with the implementation of the BI-DIME ligands for a ligand-controlled Suzuki cross-coupling and an unprecedented bis(trifluoromethane)sulfonamide-catalyzed tert-butylation renders the synthesis of this complex molecule robust, safe, and economical. Furthermore, the overall synthesis was conducted in an asymmetric and diastereoselective fashion with respect to the imbedded atropisomer.

A highly concise and convergent synthesis of HCV polymerase inhibitor Deleobuvir (BI 207127): application of a one-pot borylation-Suzuki coupling reaction.

A highly concise and convergent synthesis of HCV polymerase inhibitor Deleobuvir (BI 207127, 1) was achieved, featuring efficient Pd-catalyzed one-pot borylation-Suzuki coupling where TFP was identified as the unique ligand effective for these transformations.

Asymmetric methallylation of ketones catalyzed by a highly active organocatalyst 3,3'-F2-BINOL.

(S)-3,3'-F2-BINOL has been synthesized for the first time and demonstrated as a highly active organocatalyst for asymmetric methallylation of ketones. Up to 98:2 enantioselectivity and 99% yield were obtained with 5 mol % catalyst loading. The catalyst (S)-3,3'-F2-BINOL could be easily recovered and reused.

Palladium catalyzed alkoxy- and aminocarbonylation of vinyl tosylates.

The palladium catalyzed alkoxycarbonylation and aminocarbonylation of vinyl tosylates are described. A variety of ketone and aldehyde derived vinyl tosylates may be carbonylated in the presence of primary, secondary, and tertiary alcohols, or primary and secondary amines, to provide the corresponding esters and amides in good yields. The alkoxycarbonylation was applied to a short synthesis of isoguvacine.

Ambient temperature hydrophosphination of internal, unactivated alkynes and allenyl phosphineoxides with phosphine borane complexes.

Phosphine boranes have been found to hydrophosphinate internal, unactivated alkynes at room temperature under basic conditions without the need for catalysts or radical initiators. The use of air-sensitive secondary phosphines is avoided in this facile process. Broad scope in both the phosphine borane and alkyne partners leads to excellent diversity in the phosphine products.

Bromo-directed N-2 alkylation of NH-1,2,3-triazoles: efficient synthesis of poly-substituted 1,2,3-triazoles.

Reaction of 4-bromo-NH-1,2,3-triazoles 2 with alkyl halides in the presence of K(2)CO(3) in DMF produced the corresponding 2-substituted 4-bromo-1,2,3-triazoles 5 in a regioselective process. Subsequent Suzuki cross-coupling reaction of these bromides provided an efficient synthesis of 2,4,5-trisubstituted triazoles 3. In addition, reduction of the bromotriazoles by hydrogenation furnished an efficient synthesis of 2,4-disubstituted triazoles 8.

Asymmetric hydrogenation of unsaturated ureas with the BIPI ligands.

Asymmetric hydrogenation of unsaturated urea esters with the BIPI Ligands has been examined. Optimization of the P-N ligand structure has led to the development of chiral rhodium catalysts capable of producing the targets with >99% ee. The critical phosphine borane SNAr reaction needed for ligand synthesis has been optimized to give the adducts in high yield at ambient temperature with no racemization.

Routine histopathologic evaluation of the lacrimal sac during dacryocystorhinostomy: how useful is it?

Objective: To determine the usefulness of "routine" lacrimal sac biopsy to evaluate unsuspected neoplasm or systemic disease in patients with acquired nasolacrimal duct obstruction.

Design: Noncomparative, interventional case series with histopathologic correlation.

Participants: Review of charts revealed histopathologic reports on 302 specimens from 258 patients who had undergone routine dacryocystorhinostomy for clinical acquired nasolacrimal duct obstruction.

Nonpalpable breast carcinoma presenting as orbital infiltration: case presentation and literature review.

Purpose: To report orbital metastasis as the presenting sign of a nonpalpable breast carcinoma in a 61-year-old woman.

Methods: Case report and literature review.

Results: A uterine metastasis of unknown origin found 11 years prior was retrospectively identified as having the same histopathology as the breast and orbit tumors.