A rhodium-catalyzed asymmetric isomerization of racemic alpha-arylpropargyl alcohols to beta-chiral indanones has been developed. High enantioselectivity has been realized by the use of a newly developed axially chiral bisphosphine ligand. This ligand is unique in the sense that its axial chirality is fixed to a single configuration upon complexation to a transition metal due to other chiral axes existing within the same molecule.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/ja056584s | DOI Listing |
Org Lett
January 2025
Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.
The utilization of β-fluoroamines as pharmaceutical components for drug development has attracted a considerable amount of interest. However, direct access to tertiary β-fluoroamines is challenging. We herein report the rhodium-catalyzed asymmetric amination of tertiary allylic trichloroacetimidates with anilines and cyclic aliphatic amines to access tertiary β-fluoroamines, where the α-carbon atom is bonded to four different substituents, in good yield with high levels of enantioselectivity.
View Article and Find Full Text PDFOrg Lett
December 2024
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, United States.
Two routes to assemble the complete tricyclic core of alopecurone C are described. In the first-generation route, an efficient synthesis of the "eastern" half of the target, including a decagram-scale rhodium-catalyzed C-H insertion reaction, was developed. When this route proved intractable for assembling the final flavanone ring, a successful second-generation route was developed from a flavanone precursor (naringenin) employing a later stage C-H insertion.
View Article and Find Full Text PDFChemistry
December 2024
Department of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.
We present a comprehensive account on the evolution of a synthetic platform for a subfamily of ent-pimaranes. For the most complex member, norflickinflimiod C, five distinct strategies relying on either cationic or radical polyene cyclizations to construct the requisite tricyclic carbon scaffold were explored. Insights from early and late stage oxidative and reductive dearomatization studies ultimately led to a mild, rhodium-catalyzed arene hydrogenation for the final synthetic route.
View Article and Find Full Text PDFOrg Lett
December 2024
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 311121, P. R. China.
Catalytic hydrosilylation of 1,1-disubstituted enamides is one of the most challenging and synthetically useful processes in organosilicon chemistry and asymmetric catalysis. Herein, we report a rhodium-catalyzed enantioselective hydrosilylation of α-arylenamides with substituted hydrosilanes with the aid of chiral P-ligand, including newly developed spirophosphite ligands, giving various chiral β-silylated amides in excellent yields with good to excellent enantioselectivities (98:2 er after recrystallization). In addition, chiral β-silylated amines can be obtained by further functionalization of the hydrosilylation product.
View Article and Find Full Text PDFJ Org Chem
December 2024
Université de Bourgogne, UFR des Sciences et Techniques, ICMUB UMR-CNRS 6302, BP 47870, 21078 Dijon Cedex, France.
Chiral diphosphines with a biphenyl bridge and the chirality borne by the phosphorus atoms and not due to the atropoisomery of the biaryl backbone have been scarcely studied. Herein, we report the asymmetric synthesis of the (,)-2,2'-bis(ferrocenylphenylphosphino)biphenyl (BipheP*) ligand and its application in Rh-catalyzed hydrogenation. The synthesis was based on the enantioselective preparation of P-chirogenic ferrocenyl(-bromophenyl)phenylphosphine by the reaction of -phosphine-borane with 1,2-dibromobenzene and its homocoupling into BipheP*.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!