The use of a non-coordinating solvent for the aza-Claisen rearrangement of delta,epsilon-disubstituted acetimidates switches on a substrate directing effect that gives excellent stereoselectivity.
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Diversity-oriented synthesis of stereodefined tetrasubstituted alkenes via a modular alkyne gem-addition strategy.
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School of Pharmacy, Nanjing University of Chinese Medicine, Nanjing, China.
Stereocontrolled construction of tetrasubstituted olefins has been an attractive issue yet remains challenging for synthetic chemists. In this manuscript, alkynyl selenides, when treated with ArBCl, are subject to an exclusive 1,1-carboboration, affording tetrasubstituted alkenes with excellent levels of E-selectivity. Detailed mechanistic studies, supported by DFT calculations, elucidates the role of selenium in this 1,1-addition process.
View Article and Find Full Text PDFEnantiocontrolled Cyclization to Form Chiral 7- and 8-Membered Rings Unified by the Same Catalyst Operating with Different Mechanisms.
J Am Chem Soc
January 2025
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
Chiral medium-sized rings, albeit displaying attractive properties for drug development, suffer from numerous synthetic challenges due to difficult cyclization steps that must take place to form these unusually strained, atropisomeric rings from sterically crowded precursors. In fact, catalytic enantioselective cyclization methods for the formation of chiral seven-membered rings are unknown, and the corresponding eight-membered variants are also sparse. In this work, we present a substrate preorganization-based, enantioselective, organocatalytic strategy to construct seven- and eight-membered rings featuring chirality that is intrinsic to the ring in the absence of singular stereogenic atoms or single bond axes of chirality.
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Org Lett
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Graduate School of Life Sciences, Tohoku University, 2-1-1 Katahira, 980-8577 Aoba-ku, Sendai, Japan.
Our efforts toward the synthesis of the marine natural product portimine are described. The key to the synthesis of the skeleton is a stereoretentive copper-catalyzed C()-C() Stille-type cross-coupling that enables the convergent assembly of functionalized fragments. The core skeleton of portimine was constructed via ring-closing metathesis and transannular acetal formation.
View Article and Find Full Text PDFReactivity of Anomalous Aziridines for Versatile Access to High Fsp Amine Chemical Space.
Acc Chem Res
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Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706, United States.
ConspectusThe manipulation of strained rings is a powerful strategy for accessing the valuable chemical frameworks present in natural products and active pharmaceutical ingredients. Aziridines, the smallest N-containing heterocycles, have long served as building blocks for constructing more complex amine-containing scaffolds. Traditionally, the reactivity of typical aziridines has been focused on ring-opening by nucleophiles or the formation of 1,3-dipoles.
View Article and Find Full Text PDFA Regio- and Stereoselective Ring-Opening Polymerization Approach to Isotactic Alternating Poly(lactic-co-glycolic acid) with Stereocomplexation.
Angew Chem Int Ed Engl
January 2025
Sichuan University - Wangjiang Campus: Sichuan University, Chemistry, 29 Wangjiang Rd, 610064, Chengdu, CHINA.
Poly(lactic-co-glycolic acid) (PLGA) has been widely employed for various biomedical applications owing to its biodegradability and biocompatibility. The discovery of the stereocomplex formation between enantiomeric alternating PLGA pairs underscored its potential as high-performance biodegradable materials with diverse material properties and biodegradability. Herein, we have established a regio- and stereoselective ring-opening polymerization approach for the synthesis of stereocomplexed isoenriched alternating PLGA from racemic methyl-glycolide (rac-MG).
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