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An efficient enantioselective synthesisof the chiral polycycliccholesteryl ester transfer protein (CETP) inhibitor 1has been developed. The synthesis was rendered practical for largescale via the development of a modified Hantzsch-type reaction toprepare the sterically hindered pyridine ring, enantioselective hydrogenationof hindered ketone 6utilizing novel BIBOP-amino-pyridinederived Ru complex, efficient ICl promoted lactone formation, anda BF3mediated hydrogenation process for diastereoselectivelactol reduction. This efficient route was successfully scaled toproduce multikilogram quantities of challenging CETP drug candidate 1. [ABSTRACT FROM AUTHOR]

The use of chiral phosphinamides is relatively unexplored because of the lack of a general method for the synthesis. Reported herein is the development of a general, efficient, and highly enantioselective method for the synthesis of structurally diverse P-stereogenic phosphinamides. The method relies on nucleophilic substitution of a chiral phosphinate derived from the versatile chiral phosphinyl transfer agent 1,3,2-benzoxazaphosphinine-2-oxide. These chiral phosphinamides were utilized for the first synthesis of readily tunable P-stereogenic Lewis base organocatalysts, which were used successfully for highly enantioselective catalysis. [ABSTRACT FROM AUTHOR]

P-Stereogenic chiral phosphine BI-BOP is employed for the first time as ligand to promote catalytic enantioselective synthesis of phosphoryl-substituted atropisomeric vinylarenes through a palladium−carbene pathway. This strategy utilizes 10 mol% palladium(II) acetate, 10 mol% phosphine ligand as well as a variety of N-tosylhydrazones and phosphoryl-substituted aryl bromides as the reaction partners. The desired axially chiral vinylarenes were isolated with up to 80% yield and 96:4 er, and can be further converted effectively and stereoselectively into dialkylphosphoryl-substituted atropisomeric arenes through a Grignard reaction. This protocol offers a general approach to synthesize phosphoryl-substituted atropisomeric vinylarenes with high enantiomeric purities. [ABSTRACT FROM AUTHOR]

The use of chiral phosphinamides is relatively unexplored because of the lack of a general method for the synthesis. Reported herein is the development of a general, efficient, and highly enantioselective method for the synthesis of structurally diverse P-stereogenic phosphinamides. The method relies on nucleophilic substitution of a chiral phosphinate derived from the versatile chiral phosphinyl transfer agent 1,3,2-benzoxazaphosphinine-2-oxide. These chiral phosphinamides were utilized for the first synthesis of readily tunable P-stereogenic Lewis base organocatalysts, which were used successfully for highly enantioselective catalysis. [ABSTRACT FROM AUTHOR]

Ist das S ‐ O? Die im Titel bezeichneten Molekülgerüste verfügen über eine hoch aktive und ausreichend differenzierte S ‐ O ‐ Bindung für die effiziente Synthese enantiomerenreiner Sulfinamide. Die beschriebene Methode ist praktisch und umweltverträglich und könnte als Grundlage für ein ökonomisches kommerzielles Verfahren zur Herstellung sperriger Sulfinamide dienen. [ABSTRACT FROM AUTHOR]