Although cycloadditions of bicyclobutanes (BCBs) have emerged as a reliable approach for producing bicyclo[.1.1]alkanes such as azabicyclo[3.1.1]heptanes (aza-BCHeps), serving as saturated bioisosteres of arenes, the catalytic asymmetric variant remains underdeveloped and presents challenges. Herein, we developed several Lewis acid-catalyzed systems for the challenging dearomative (3+3) cycloaddition of BCBs and aromatic azomethine imines. This resulted in fused 2,3-diazabicyclo[3.1.1]heptanes, introducing a novel chemical space for the caged hydrocarbons. Moreover, an asymmetric Lewis acid catalysis strategy was devised for the (3+3) cycloadditions of BCBs and -iminoisoquinolinium ylides, forming chiral diaza-BCHeps with up to 99% yield and 97% ee. This study showcases a unique instance of asymmetric (3+3) cycloaddition facilitated by the creation of a chiral environment the activation of BCBs.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11575549 | PMC |
| http://dx.doi.org/10.1039/d4sc06334a | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Enantioselective Synthesis of Spirooxindole-Pyran and Furan Scaffolds via Copper-Catalyzed Formal (3+3) and (3+2) Cycloaddition of Isatin-Derived Propargylic Esters.
Chemistry
December 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Uttar Pradesh, Kanpur, 208016, India.
Herein, we report a copper-catalyzed enantioselective formal (3+3) and (3+2) cycloaddition reaction of isatin-derived tertiary propargylic esters with N,N-dimethylbarbituric acid and 4-hydroxycoumarins, respectively. In this process, the tertiary propargylic ester serves as both C3- and C2-synthons, facilitating the synthesis of optically active spirooxindole-pyran and furan scaffolds featuring an all-carbon quaternary stereocenter. The reaction delivers these spirocyclic frameworks in good yields with high enantioselectivities.
View Article and Find Full Text PDFDiscovery and Chemical Exploration of Spiro[Benzofuran-3,3'-Pyrroles] Derivatives as Innovative FLT3 Inhibitors for Targeting Acute Myeloid Leukemia.
Antiinflamm Antiallergy Agents Med Chem
December 2024
Chemistry Department, Faculty of Science, The University of Jordan, Amman, 11942, Jordan.
Aims: This study aimed at the synthesis of several spiro[benzofuran-3,3'-pyrroles] derivatives by a three-component reaction conducted by mixing DMAD, N-bridgehead het-erocycles, and benzofuran-2,3-diones in dichloromethane at room temperature for 24 h. Moreover, in vitro evaluation of their cytotoxicity affinities against FMS-like tyrosine kinase 3 was carried out.
Objectives: The objective of this study was to use a one-pot, three-component reaction to synthesize a novel set of spiro[benzofuran-3,3'-pyrroles] derivatives.
A Multifunctional Tb(III)-Based Metal-Organic Framework for Chemical Conversion of CO, Fluorescence Sensing of Trace Water and Metamitron.
Inorg Chem
December 2024
School of Materials Science and Chemical Engineering, Resource Recycling of Ningbo University - Ningbo Shuangneng Environmental Technology Co., Ltd., Ningbo University, Ningbo 315211, China.
The utilization of metal-organic frameworks (MOFs) as fluorescent sensors for the detection of environmental and chemical reagent pollutants as well as heterogeneous catalysis for CO conversion represents a crucial avenue of research with significant implications for the protection of human health. In this work, a Tb(III)-based three-dimensional metal-organic framework, [Tb(L)·4DMF] (Tb-MOF) (HL = 5'-(4-carboxy-3-hydroxyphenyl)-3,3″-dihydroxy-[1,1':3',1″-terphenyl]-4,4″-dicarboxylic acid), has been structurally conformed by single-crystal X-ray crystallography. It possesses a 1D rhombus channel along the [010] direction, featuring a pore size of 6.
View Article and Find Full Text PDFDouble Strain-Release (3+3)-Cycloaddition: Lewis Acid Catalyzed Reaction of Bicyclobutane Carboxylates and Aziridines.
Chemistry
December 2024
Albert-Ludwigs-Universität Freiburg, Institute of Organic Chemistry, Albertstraße 21, 79104, Freiburg, Germany.
A (3+3)-cycloaddition to afford 2-azabiyclo[3.1.1]heptanes was realized by reacting highly strained aryl bicyclo[1.
View Article and Find Full Text PDFA DFT Study on the NHC-Catalyzed Reaction of Enals with Aminoacrylates: Mechanism, Regioselectivity, and Stereoselectivity.
J Phys Chem A
December 2024
School of Chemical Engineering, University of Science and Technology Liaoning, Qianshan Road 185, Anshan 114051, Liaoning, China.
Article Synopsis
- DFT (M06-2X) calculations reveal the mechanism of NHC-catalyzed [3 + 3] cycloaddition involving enals and aminoacrylates, starting with NHC binding to an enal and leading to a series of intermediates.
- The critical step in the reaction is the formation of a new C-C bond in the acyl azolium intermediate, which dictates the stereoselectivity, favoring the -face addition and producing a specific -configuration.
- The final product, dihydropyridinone, shows a calculated enantiomeric excess of 99.1%, closely matching experimental results, with enantioselectivity linked to strong interactions in the transition state.
Want AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!