A novel tandem Mannich/intramolecular aminal formation between tryptamines and salicylaldehydes was reported. This strategy provides a promising approach for the stereoselective synthesis of a range of complex fused spiroindolines, which bear a highly congested contiguous spiro quaternary center and two tertiary stereocenters, in a highly economical and effective fashion.
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http://dx.doi.org/10.1021/jo302404v | DOI Listing |
Angew 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 PDFBiotechnol Notes
December 2024
Centre for Molecular Biology, Central University of Jammu, Rahya Suchani (Bagla), Jammu & Kashmir, India.
The amidases (EC 3.5.1.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Organic Chemistry Division, CSIR-National Chemical Laboratory, Dr Homi Bhabha Road, Pune-411008, India.
We report the stereoselective total synthesis of kavaratamide A, a linear lipodepsipeptide from the cyanobacterium (collected in Kavaratti, India), and its unnatural C25-epimer. The convergent approach employs Keck asymmetric allylation to construct the chiral β-hydroxy carboxylic acid fragment [(3)-HDA; 3-hydroxydecanoic acid], while the peptide unit was assembled from L-Val, -Me-L-Ala, ()-Hiva, and ()-Pr--Me-pyr using well-orchestrated coupling methods to prevent racemization. Modifications to the Keck allylation conditions enabled the synthesis of the C25-epimer with good yield.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Jain University - Ramanagara Campus, Centre for Nano and Material Sciences, Jakkasandra Post Kanakapura Taluk, Ramanagara-562112, Bangalore, 562112, Bangalore, INDIA.
The development of a metallic copper-based catalyst system remains a significant challenge. Herein, we report the synthesis of highly stable, active, and reusable Cu0 catalyst for the carboboration of alkynes using carbon electrophiles and bis(pinacolato)diboron (B2pin2) as chemical feedstocks to afford di- and trisubstituted vinylboronate esters in a regio- and stereoselective manner with appreciable turnover number (TON) of up to 2535 under mild reaction conditions. This three-component coupling reaction works well with a variety of substituted electrophiles and alkynes with broad functional group tolerance.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
School of Chemistry and Chemical Engineering, Key Laboratory of Colloid and Interface Chemistry of the Ministry of Education, Shandong University, Jinan 250100, P. R. China.
Herein, we describe a hexavalent tellurium-based chalcogen bonding catalysis platform capable of addressing reactivity and selectivity issues. This research demonstrates that hexavalent tellurium salts can serve as a class of highly active chalcogen bonding catalysts for the first time. The tellurium centers in these hexavalent catalysts have only one exposed interaction site, thus providing a favorable condition for the controlling of reaction selectivity.
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