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Chiral imidodiphosphoric acids were employed as efficient catalysts in the enantioselective addition reaction of pyrrole and indoles to 3-vinylindoles. A series of optically active 1,1,1-triarylethmanes bearing quaternary stereocenters were synthesized in excellent yields (up to 99% yield) and enantioselectivities (up to 98% ee). Gram-scale reactions of and as well as and demonstrated the synthetic utility of this methodology. Control experiments showed that the formation of a double H-bond between the catalyst and substrates is necessary for an excellent outcome.
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http://dx.doi.org/10.1021/acs.joc.9b02024 | DOI Listing |
Angew Chem Int Ed Engl
January 2023
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, 200240, China.
Chiral imidodiphosphates (IDPs) have emerged as strong Brønsted acid catalysts for many enantioselective processes. However, the dynamic transformation between O,O-syn and O,O-anti conformers typically results in low enantioselectivity. Here we demonstrate that topologies of metal-organic frameworks (MOFs) can be exploited to control IDP conformations and local chiral microenvironments for enantioselective catalysis.
View Article and Find Full Text PDFAn efficacious method in which BINOL-type chiral imidodiphosphoric acid catalyzed the asymmetric [5 + 1] annulation reaction of 2-pyrrolylphenol with 1-methylindoline-2,3-dione was established. The strategy tolerated a broad substrate scope, and 30 examples were obtained. A range of enantioenriched spiro[3,2'-morpholine-oxindole] derivatives which incorporate a tertiary stereocenter, with moderate to excellent yields (up to 96%) and enantioselectivities (up to 99%) under mild conditions, was delivered.
View Article and Find Full Text PDFOrg Lett
September 2021
Key Laboratory of Applied Chemistry of Chongqing Municipality, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
The unique structure of oxyallyls represents a significant challenge for their catalytic asymmetric applications. Herein, an unprecedented chiral imidodiphosphoric acid-catalytic enantioselective (3 + 3) cycloaddition between oxyallyl zwitterions generated from α-haloketones and α-diazomethylphosphonates was developed. Pharmaceutically interesting chiral pyridazine-4()-ones were obtained in up to 98% yields with excellent stereoselectivities (up to 99% ee, > 99:1 dr).
View Article and Find Full Text PDFOrg Lett
June 2021
College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China.
The development of a stereoselective method for the rapid assembly of structurally complex molecules remains fascinating and challenging in synthetic organic chemistry. Here, we report an enantioselective domino reaction between 3-vinylindole and -quinone methide for the preparation of 3-indolyl cyclopenta[]indoles containing multiple chiral centers. Chiral imidodiphosphoric acids enable this cascade asymmetric process, delivering a series of products with excellent yields (≤99%), enantioselectivities (≤99%), and diastereoselectivities (≤20:1 dr).
View Article and Find Full Text PDFJ Am Chem Soc
November 2020
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. China.
A radical-based asymmetric olefin difunctionalization strategy for rapidly forging all-carbon quaternary stereocenters α to diverse azaarenes is reported. Under cooperative photoredox and chiral Brønsted acid catalysis, cyclopropylamines with α-branched 2-vinylazaarenes can undergo a sequential two-step radical process, furnishing various valuable chiral azaarene-substituted cyclopentanes. The use of the rigid and confined -symmetric imidodiphosphoric acid catalysts achieves high enantio- and diastereo-selectivities for these asymmetric [3 + 2] cycloadditions.
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