The first [4 + 2] cyclizations of para-quinone methide derivatives with isocyanates have been established under the catalysis of Brønsted acids or Brønsted bases, which efficiently constructed benzoxazin-2-one frameworks in generally high yields (up to 95%). This reaction will not only enrich the research contents of para-quinone methide-involved cyclization reactions but also provide a useful method for constructing biologically important benzoxazin-2-one frameworks.
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http://dx.doi.org/10.1039/c9ob00918c | DOI Listing |
Org Lett
October 2024
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand 247667, India.
Herein, we evolve a base-promoted synthesis of 2-chromen-2-one and chromeno[2,3-]pyrrole scaffolds via (4 + 2) annulation of α-alkylidene succinimides with 2-hydroxyphenyl-substituted -quinone methides (-QMs). Extremely selective and switchable cyclizations were obtained by modifying the base. This metal-free protocol is highlighted by its mild reaction conditions and broad substrate scope, and the viability of the existing protocol was additionally illustrated by gram-scale synthesis and further modification.
View Article and Find Full Text PDFWe herein report a two-step protocol for the asymmetric synthesis of novel chiral benzofused ϵ-lactones starting from O-protected hydroxymethyl-para-quinone methides and activated aryl esters. By using chiral isothiourea Lewis base catalysts a broad variety of differently substituted products could be obtained in yields of around 50 % over both steps with high levels of enantioselectivities, albeit low diastereoselectivities only.
View Article and Find Full Text PDFOrg Biomol Chem
November 2023
Program on Chemical Sciences, Chulabhorn Graduate Institute, Center of Excellence on Environmental Health and Toxicology (EHT), OPS, MHESI, 54 Kamphaeng Phet 6, Laksi, Bangkok 10210, Thailand.
Our research has led to the development of a divergent synthesis approach for the synthesis of 3,4-dihydro-2-benzo[]chromen-2-one 3 and fluorenone 9 derivatives using -alkynylarylketones as common precursors. The synthesis of 3,4-dihydro-2-benzo[]chromen-2-ones 3 employed silver catalyzed ketonization to form polycarbonyl intermediates which underwent double intramolecular cyclization and decarboxylation to generate a lactone and a phenyl ring in a one-pot fashion. In addition, the same precursor could be used to prepare fluorenone derivatives 9 under acidic conditions.
View Article and Find Full Text PDFJ Org Chem
July 2023
Department of Chemistry, Savitribai Phule Pune University (Formerly University of Pune), Ganeshkhind, Pune 411007, India.
A facile one-pot metal-free, base-mediated formal [3 + 2] and [4 + 2] dearomative -cycloaddition of -quinone methides (-QMs) with halo alcohols has been designed for the efficient construction of 2-oxa-spirocyclohexadienones in excellent yield under mild reaction conditions. The commercial availability of the bases, reagents, and convenient reaction procedure makes it an attractive method for -cyclization.
View Article and Find Full Text PDFChem Commun (Camb)
July 2023
State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Key Laboratory of Green Pesticides and Cleaner Production Technology of Zhejiang Province, Department of Green Chemistry and Technology, Zhejiang University of Technology, Hangzhou 310014, P. R. China.
A sequential asymmetric conjugate addition/cyclisation of α-bromohydroxamates with -quinone methide derivatives has been developed, which provides enantioenriched 1,4-benzoxazepines in generally high yields (up to 95%) and good enantioselectivities (up to 97 : 3 er). This protocol not only offers a novel and straightforward strategy for constructing chiral 1,4-benzoxazepines, but also demonstrates the potential of α-bromohydroxamates as three-atom synthons in asymmetric cyclisation reactions.
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