C-H activation-based ring-forming methods are a powerful approach for the construction of complex molecular architectures, especially those containing a congested stereocenter. Therefore, this strategy seems perfectly suited to address the synthesis of chiral polycyclic aromatic hydrocarbons (PAHs) and bowl-shaped molecules, which are important target molecules in the field of organic electronic materials. Herein, we describe an enantioselective Pd -catalyzed C(sp )-H arylation protocol for the synthesis of chiral fluoradenes and other warped molecules, which could serve to the bottom-up construction of chiral PAHs. The current approach relies on the use of chiral bifunctional phosphine-carboxylate ligands and delivers diverse polycyclic compounds in high yield and with good to excellent enantioselectivity. The chiroptical properties of the obtained products were investigated, and some of them were found to have a strong ellipticity and an emission band located in the visible region.
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http://dx.doi.org/10.1002/anie.202013303 | DOI Listing |
J Am Chem Soc
January 2025
National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, P. R. China.
Due to their strong aromaticity and difficulties in chemo-, regio-, and enantioselectivity control, asymmetric hydrogenation of naphthol derivatives to 1,2,3,4-tetrahydronaphthols has remained a long-standing challenge. Herein, we report the first example of homogeneous asymmetric hydrogenation of naphthol derivatives catalyzed by tethered rhodium-diamine catalysts, affording a wide array of optically pure 1,2,3,4-tetrahydronaphthols in high yields with excellent regio-, chemo-, and enantioselectivities (up to 98% yield and >99% ee). Mechanistic studies with experimental and computational approaches reveal that fluorinated solvent 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) plays vital roles in the control of reactivity and selectivity, and 1-naphthol is reduced via a cascade reaction pathway, including dearomative tautomerization, 1,4-hydride addition, and 1,2-hydride addition in sequence.
View Article and Find Full Text PDFJ Org Chem
January 2025
State Key Laboratory of Fine Chemicals, Department of Pharmaceutical Engineering, School of Chemical Engineering, Dalian University of Technology, 2 Linggong Road, Dalian 116024, China.
This paper presents a new strategy for the construction of the chiral 4-chromene skeleton. A series of chiral 2-trifluoromethyl-4-(indol-3-yl)-4-chromenes were synthesized in moderate to good yields (60-92%) with excellent enantioselectivity (up to 97% ee) through the palladium-catalyzed asymmetric condensation of 2-chromenes and indoles. These trifluoromethylated, stereochemically rich building blocks hold potential value in medicinal chemistry.
View Article and Find Full Text PDFChem Rec
January 2025
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing University, Chongqing, 401331, P. R. China.
Since the introduction of the concept of inherent chirality by Böhmer, an important part of research focused on the asymmetric synthesis of calixarene macrocycles. However, long synthetic procedures and tedious separation strategies hampered the application of this technology in many topics of organic chemistry, including enantioselective molecular recognition and catalysis. Very recently, a new generation of enantioselective catalytic methodologies has been reported, able to provide highly functionalized, inherently chiral calixarenes in a straightforward manner.
View Article and Find Full Text PDFNat Chem
January 2025
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, China.
The substitution of an aromatic ring with a C(sp)-rich bicyclic hydrocarbon, known as bioisosteric replacement, plays a crucial role in modern drug discovery. Substituted bicyclo[1.1.
View Article and Find Full Text PDFJ Org Chem
January 2025
Institute for Research in Biomedicine (IRB Barcelona). The Barcelona Institute of Science and Technology (BIST), Baldiri Reixach 10, 08028 Barcelona, Spain.
A novel chiral ligand, named MAdPHOS, bearing a P-stereogenic phosphane and a diadamantyl phosphane linked by a NH bridge has been synthesized. This bulky, C-symmetric, PNP ligand has been prepared from enantiopure -butylmethyl aminophosphane and was obtained as a crystalline solid. The NH/PH tautomerism, air-stability, and σ-donor capacity of MAdPHOS have been assessed herein.
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