A diastereoselective 1,3-dipolar cycloaddition reaction between trifluoroethyl amine-derived isatin ketimines and chalcones was successfully achieved in the presence of DBU. A series of 5'-CF-substituted 3,2'-pyrrolidinyl spirooxindoles were efficiently synthesized with high yields and excellent diastereoselectivities (up to 89% yield, and >99 : 1 dr). The anticancer activities of these highly functionalized spiro[pyrrolidin-3,2'-oxindole] derivatives were evaluated.
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http://dx.doi.org/10.1039/d3ra08127c | DOI Listing |
J Org Chem
January 2025
Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
Nucleophilic substitution reactions of C-2-acyloxy furanosyl acetals can be highly diastereoselective. We here show that the presence of a less electron-donating -nitrobenzoyloxy group at C-2 of a furanosyl acetal can be of use to control the 1,2- stereoselectivity of acetal substitution reactions with higher stereoselectivity than the analogue with the more electron-donating benzoyloxy group, just as what was observed in the pyranosyl system. Computational results support a reaction manifold involving both open oxocarbenium ions and -dioxolenium ions to provide the 1,2- and 1,2- products.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Department of Chemistry, Western Washington University, Bellingham, WA 98225, USA.
Vinylic phenylsulfones containing a β-hydroxyl stereocenter undergo a diastereoselective isomerization to the corresponding allylic isomer upon treatment with 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Shanghai Institute of Materia Medica Chinese Academy of Sciences, Chemical Biology Research Center, 201203, Shanghai, CHINA.
Aldolases are powerful C-C bond-forming enzymes for asymmetric organic synthesis because of their supreme stereoselectivity, diverse electrophiles and nucleophiles, and promising scalability. Stereodivergent engineering of aldolases to tune the selectivity for the synthesis of stereoisomers of chiral molecules is highly desirable but has rarely been reported. This study documented the semirational engineering of the decarboxylative aldolase UstD with the focused rational iterative site-specific mutagenesis (FRISM) strategy to perform a C-C bond-forming reaction with dione electrophiles.
View Article and Find Full Text PDFOrg Lett
January 2025
Jiangsu Key Laboratory of Pesticide Science and Department of Chemistry, College of Sciences, Nanjing Agricultural University, Nanjing, 210095, P. R. China.
Radical-initiated functionalization of bicyclo[1.1.0]butanes (BCBs) is a straightforward approach to accessing diverse cyclobutane derivatives.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Institute of Organic Chemistry, University of Leipzig, 04103 Leipzig, Germany.
The enantioselective synthesis of 1,4-dicarbonyl compounds continues to pose a significant challenge in organic synthesis, and a catalytic process which generates two adjacent stereogenic centers with full stereochemical control is lacking until now. The 1,4-relationship of the functional groups requires an Umpolung strategy as one of the α-carbonyl positions has to be inverted into an electrophilic center to react with a normal enolate. We report herein the highly enantio- and diastereoselective addition of silyl ketene acetals toward electrophilic 1-azaallyl cations to furnish chiral 4-hydrazonoesters, which are masked 1,4-dicarbonyl compounds.
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