The synthesis of cyclic imidazolidines via two N-C bond-forming sequences has been developed. The transformation goes through a (3 + 2)-cycloaddition reaction in the presence of catalytic amounts of palladium by combining several vinyl aziridines and cyclic N-sulfonyl imines. Interestingly, the use of LiCl as additive allowed the improvement of diastereoselectivities when less encumbered substrates were used. The imidazolidine derivatives that bear aminal cores are isolated in high yields (15 examples, up to 96% yield) and diastereoselectivities (up to >20:1).
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.8b00228 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Regioselective Palladium-Catalyzed Chain-Growth Allylic Amination Polymerization of Vinyl Aziridines.
J Am Chem Soc
June 2024
Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599, United States.
Organometallic-mediated chain growth polymerization of readily accessible chemical building blocks is responsible for important commercial and technological advances in polymer science, but the incorporation of heteroatoms into the polymer backbone through these mechanisms remains a challenge. Transition metal π-allyl complexes are well-developed organometallic intermediates for carbon-heteroatom bond formation in small-molecule catalysis yet remain underexplored in polymer science. Here, we developed a regioselective palladium-phosphoramidite-catalyzed chain-growth allylic amination polymerization of vinyl aziridines for the synthesis of novel nitrogen-rich polymers via ambiphilic π-allyl complexes.
View Article and Find Full Text PDFRecent updates on vinyl cyclopropanes, aziridines and oxiranes: access to heterocyclic scaffolds.
Org Biomol Chem
May 2024
Department of Chemistry, National Institute of Technology, Tiruchirappalli, Tiruchirappalli-620 015, Tamil Nadu, India.
This present review delineates the repertoire of vinyl cyclopropanes and their stuctural analogues to accomplish a wide array of oxa-cycles, aza-cycles, and thia-cycles under transition metal catalysis and metal-free approaches from early 2019 to the present date. The generation of electrophilic π-allyl intermediates and 1-3/1-5-dipolarophile chemistry originating from VCPs are always green, step- and atom-economical and sustainable strategies in comparsion with prefunctionalized and/or C-H activation protocols. Here, the strained ring-system extends its applicability by relieving the strain to undergo a ring-expansion reaction to accomplish 5-9 membered carbo- and heterocyclic systems.
View Article and Find Full Text PDFEnantioselective Total Synthesis of (-)-Hunterine A Enabled by a Desymmetrization/Rearrangement Strategy.
J Am Chem Soc
February 2024
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
The first enantioselective total synthesis of (-)-hunterine A is disclosed. Our strategy employs a catalytic asymmetric desymmetrization of a symmetrical diketone and subsequent Beckmann rearrangement to construct a 5,6-α-aminoketone. A convergent 1,2-addition joins a vinyl dianion nucleophile and the enantioenriched ketone.
View Article and Find Full Text PDFRhodium-Catalyzed One-Carbon Ring Expansion of Aziridines with Vinyl-N-triftosylhydrazones for the Synthesis of 2-Vinyl Azetidines.
Angew Chem Int Ed Engl
March 2024
Department of Chemistry, Northeast Normal University, 130024, Changchun, China.
Azetidines, being four-membered N-heterocycles, possess significant potential in contemporary medicinal chemistry owing to their favorable pharmacokinetic properties. Regrettably, the incorporation of functionalized azetidines into pharmaceutical lead structures has been impeded by the absence of efficient synthetic methods for their synthesis. In this study, a Rh-catalyzed one-carbon ring expansion of aziridines with vinyl-N-triftosylhydrazones is presented, which facilitates the synthesis of high value-added 2-alkenyl azetidine products.
View Article and Find Full Text PDFCopper(I)-Photocatalyzed Diastereoselective Aziridination of N-Sulfonyl Imines with Vinyl Azides: Application to Benzo[f][1,2,3]oxathiazepines Dioxides and Fused Isoxazolines.
Chem Asian J
January 2024
Department of Chemistry, Indian Institute of Technology Indore, Simrol, 453552, Madhya Pradesh, India.
An in situ generated photoactive copper(I)-complex-catalyzed aziridination reaction of cyclic N-sulfonyl imines with α-aryl-substituted vinyl azides irradiated by blue-LEDs light is reported for the first time. This novel SET process represents a mild, sustainable, and pragmatic method for accessing synthetically resourceful sulfamidate-fused aziridines in acceptable chemical yields with excellent diastereoselectivities. Delightedly, pharmacologically attractive benzo[f][1,2,3]oxathiazepine dioxides and fused isoxazoline frameworks were achieved through our newly developed metal-free based ring-expansion techniques, highlighting the synthetic value of accessed aziridines.
View Article and Find Full Text PDFWant 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!