The first asymmetric Michael/cyclization tandem reaction of 4-hydroxycoumarin with nitroolefins catalyzed by chiral bifunctional thioureas was reported and 2,3-dihydrofuro[3,2-c]-coumarin adducts have been obtained in moderate yields (53-75%) and good enantioselectivities (64-90% ee).
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http://dx.doi.org/10.1039/c2ob27121d | DOI Listing |
Org Biomol Chem
January 2025
Department of Chemistry, University of York, Heslington, York, UK, YO10 5DD.
3-Spiropiperidines can be synthesized in up to 87% yield and 96 : 4 er using a two step 'Clip-Cycle' approach. The 'Clip' stage of this method is based on efficient and highly -selective cross metathesis of -Cbz-protected 1-amino-hex-5-enes with a thioacrylate. This is followed by the 'Cycle' step, in which an intramolecular asymmetric aza-Michael cyclization is promoted by a chiral phosphoric acid catalyst.
View Article and Find Full Text PDFChemistry
December 2024
Department of Pharmacy, Jilin Medical University, Jilin, Jilin, 132013, China.
Asymmetric synthesis of derivatives of spiro[indoline-3,4-pyrrolo[3,4-b]pyridines] were first developed through the organocatalytic cascade of Knoevenagel/Michael/cyclization reactions using a quinidine-derived squaramide. Under the optimized conditions, the three-component reactions of isatins, cyanoacetates, and 3-aminomaleimides yield the desired heterocycle-fused spirooxindoles in good yields (78-91 %) with 53 %-99 % enantiomeric excess (ee). Notably, this reaction enables a broad substrate scope under mild conditions and provides a convenient method for the enantioselective construction of diverse spirooxindoles combined with dihydropyridine and maleimide skeletons, which has great potential for the construction of new bioactive chemical entities.
View Article and Find Full Text PDFSarglamides A-E were identified as a structurally new class of alkaloids with potential application for inflammation-associated diseases. Reported is the first asymmetric total synthesis of sarglamides A, C, D, E, and F within 7 steps, featuring an intermolecular Diels-Alder cycloaddition of ()-phellandrene and 1,4-benzoquinone and intramolecular (-)Michael addition to construct the tetracyclic core of sarglamides. Importantly, our work demonstrated that the hypothetic Diels-Alder reaction of α-phellandrene with dienophile toussaintine C (or analogues) originally proposed as a biosynthetic pathway was not viable under non-enzymatic conditions.
View Article and Find Full Text PDFChem Commun (Camb)
August 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, Uttar Pradesh, India.
The first metal-catalyzed (2+4) annulation of 5-alkenyl thiazolones and α,α-dicyanoalkylidenes has been developed vinylogous Michael/cyclization/isomerization reaction. This (2+4) annulation reaction is catalyzed by a chiral Ag-()-DTBM-SEGPHOS catalyst, delivering enantioenriched spiro[cyclohexenamines-thiazolone] having contiguous quaternary and tertiary stereocenters in good to excellent yield (up to 80%) and excellent stereoselectivities (up to 97% ee and >20 : 1 dr). This methodology has high functional group tolerance and produces a broad range of enantioenriched products under mild reaction conditions.
View Article and Find Full Text PDFJ Org Chem
June 2024
Department of Chemistry, National Chung Hsing University, Taichung City 40227, Taiwan, R.O.C.
Two substrate-controlled regiodivergent annulation protocols for 2,3-dioxopyrrolidines with 3-alkylidene oxindoles have been developed, which furnished a series of fused dihydropyrrolidone derivatives in high yields with excellent stereoselectivities. Plausible mechanistic pathways for both annulation reactions are proposed that [3 + 3] annulation reaction involves vinylogous Michael addition followed by intramolecular aldol cyclization, while [4 + 2] annulation reaction occurs through a vinylogous Michael addition and a subsequent intramolecular -Michael cyclization.
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