Herein, we report acid-mediated divergent annulations of (-aryl)-alkynyl sulfonamides. The substituent at the position of the -aryl group determines two diverse reaction paths, leading to the selective assembly of benzo-fused sultams and spirocyclic sultams. This strategy provides a series of benzo/spiro-sultams with wide functional group compatibility and good to excellent yields under mild reaction conditions. Additionally, scale-up reaction and further transformations of the products were also carried out to demonstrate the utility of the protocol.
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http://dx.doi.org/10.1021/acs.joc.4c01517 | DOI Listing |
J Org Chem
October 2024
Department of Organic Synthesis & Process Chemistry, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad 500007, India.
Herein, we report acid-mediated divergent annulations of (-aryl)-alkynyl sulfonamides. The substituent at the position of the -aryl group determines two diverse reaction paths, leading to the selective assembly of benzo-fused sultams and spirocyclic sultams. This strategy provides a series of benzo/spiro-sultams with wide functional group compatibility and good to excellent yields under mild reaction conditions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2024
School of Chemistry, Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, and Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, Sun Yat-Sen University, Guangzhou, 510006, P. R. China.
Given the tremendous success of (p-cymene)Ru-catalyzed C-H activation over the past 20 years, the community has long been aware that the development of chiral η-benzene (Ben) ligands should be a potent strategy for achieving the attractive but incredibly underdeveloped ruthenium(II)-catalyzed asymmetric C-H activation. However, it has rarely been achieved due to the severe difficulty in developing proper chiral Ben ligands. In particular, designing chiral Ben ligands by connecting a benzene fragment to a chiral framework including benzene rings remained an unsolved challenge until this effort.
View Article and Find Full Text PDFEuropean J Org Chem
December 2021
Enamine Ltd. (www.enamine.net), Chervonotkatska Street 78, Kyiv 02094, Ukraine.
One-pot intramolecular cyclization of novel sp-enriched cyanoalkylsulfonyl fluorides into spirocyclic β- or γ-sultams is disclosed. The method relies on nitrile group reduction followed by sulfonylation of amino group thus formed upon mild conditions (NaBH, NiCl·6HO in MeOH). Cyclization proceeds smoothly with considerable efficiency (48-84%, 10 examples) on up to 30 g scale.
View Article and Find Full Text PDFJ Org Chem
August 2021
NMPA Key Laboratory for Research and Evaluation of Innovative Drug, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, China.
Presented herein is an effective preparation of succinimide spiro-fused sultams through the coupling reaction of -(phenylsulfonyl)acetamides with maleimides. It is deduced that this reaction should proceed through a cascade process including Rh(III)-catalyzed C(sp)-H bond cleavage of -(phenylsulfonyl)acetamide, maleimide double bond insertion into the C-Rh bond, β-hydride elimination, reductive elimination, and intramolecular aza-Michael addition. Notably, this cascade procedure features simultaneous annulation and spirocyclization through traceless fusion of the directing group into target product by using air as an economical oxidant to assist the regeneration of the active Rh(III) catalyst.
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