Bifunctional chiral squaramide-catalyzed highly enantioselective Michael addition of nitromethane to diverse 2-enoylazaarenes was successfully performed. This protocol provided a set of chiral azaarene-containing γ-nitroketones with up to 98% yield and 98% ee in a solvent-free catalytic system under mild conditions. Furthermore, gram-scale synthetic utility was also showcased.
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http://dx.doi.org/10.1039/d4ra03826f | DOI Listing |
Chemistry
December 2024
Department of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.
We present a comprehensive account on the evolution of a synthetic platform for a subfamily of ent-pimaranes. For the most complex member, norflickinflimiod C, five distinct strategies relying on either cationic or radical polyene cyclizations to construct the requisite tricyclic carbon scaffold were explored. Insights from early and late stage oxidative and reductive dearomatization studies ultimately led to a mild, rhodium-catalyzed arene hydrogenation for the final synthetic route.
View Article and Find Full Text PDFOrg Lett
December 2024
Department of Medicinal Chemistry, University of Kansas, Lawrence, Kansas 66047, United States.
We show the first examples of enantioselective cyclization reactions of tethered sulfamates onto pendant α,β-unsaturated esters, ketones, and thioesters. This reaction is promoted by a new chiral bifunctional guanidine catalyst and is operationally very simple. A variety of primary sulfamates and sulfamides were examined, and in many cases, products were delivered in excellent yields and enantiomeric ratios.
View Article and Find Full Text PDFJ Org Chem
December 2024
Institute and State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, P. R. China.
An asymmetric tandem esterification/Michael addition reaction of β-keto acylpyrazoles with -hydroxychalcones has been established under the catalysis of a bifunctional squaramide-tertiary amine. A wide variety of biorelevant 3,4-dihydrocoumarin derivatives were generally obtained in high yields (up to 93%) with excellent diastereo- and enantioselectivities (>19:1 dr, up to 93% ee) under mild reaction conditions. This reaction represents the successful application of β-keto acylpyrazoles as 2C building blocks in catalytic asymmetric cyclizations.
View Article and Find Full Text PDFAdv Sci (Weinh)
November 2024
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou, 310018, China.
Chiral fully-substituted allenes are synthetically significant and pivotal building blocks that can engage in diverse transformations toward a variety of bioactive molecules. The enantioselective assembly of these skeletons using readily available reactants offers significant advantages but remains challenging. Herein, an asymmetric formal Michael-type addition of alkynyl imines with the key alkylgold intermediates derived in situ from N-propargylamides is accomplished under gold-complex and chiral quinine-derived squaramide (QN-SQA) synergetic catalysis.
View Article and Find Full Text PDFJ Org Chem
December 2024
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China.
An organocatalytic asymmetric vinylogous Michael/oxa-Michael tandem reaction between β,γ-unsaturated pyrazoleamides and isatin-derived β,γ-unsaturated ketoesters has been developed with excellent regio-, diastereo-, and enantioselectivities. The methodology provides an effective approach to construct enantiomerically pure 3,4'-pyranyl spirooxindole derivatives containing three contiguous chiral centers. Moreover, the transformations of the chiral products, including the removal and reduction of the pyrazole group, have been investigated.
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