A regiodivergent synthesis of functionalized indene derivatives from a Pt-catalyzed Rautenstrauch reaction of propargyl carbonate is described. A one-pot Rautenstrauch/Tsuji-Trost reaction delivering 2-indanones was realized efficiently using this methodology.
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http://dx.doi.org/10.1021/ol300158d | DOI Listing |
J Org Chem
January 2025
School of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu 241000, PR China.
-Iodosuccinimide-promoted cascade reactions of arylidene isoxazolones with amidines in -xylene were accomplished, affording 5-acylimidazoles in good to excellent yields. Interestingly, when the reactions were performed by employing acetonitrile as the solvent, 4-acylimidazoles were efficiently obtained. Mechanistic studies indicate that the formation of imidazolyl and acyl moieties may undergo a spiroannulation-ring opening aromatization-hydrolysis cascade reaction sequence.
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 PDFJ Am Chem Soc
January 2025
Key Laboratory of Chemical Biology of Fujian Province, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
Regiodivergent asymmetric synthesis represents a transformative strategy for the efficient generation of structurally diverse chiral products from a single set of starting materials, significantly enriching their enantiomeric composition. However, the design of radical-mediated regiodivergent and enantioselective reactions that can accommodate a wide range of functional groups and substrates has posed significant challenges. The obstacles primarily lie in switching the regioselectivity and achieving high enantiodiscrimination, especially when dealing with high-energy intermediates.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry and Biochemistry, Loyola University Chicago, Chicago, Illinois 60660, United States.
Angew Chem Int Ed Engl
December 2024
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Key Laboratory of Organosilicon Material Technology of Zhejiang Province, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, 2318 Yuhangtang Road, Hangzhou, 311121, P. R. China.
In industry, the two important nitrile starting materials, adiponitrile and 2-methylglutaronitrile, are primarily manufactured through the well-known DuPont process, which consists of a tandem sequence including first hydrocyanation, isomerization and second hydrocyanation. However, this mature process has the intrinsic defects of step efficiency and regioselectivity. Herein, we report a nickel-catalyzed divergent, one-step double hydrocyanation of 1,3-butadiene to produce either adiponitrile or 2-methylglutaronitrile in high regioselectivity.
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