The dearomative introduction of trifluoromethyl and 1,1-difluoroethyl radicals, generated from their corresponding sulfinate salts, into the C2 position of indole derivatives allows the diastereoselective synthesis of three-dimensional 3,3-spirocyclic indolines over C-H functionalized indoles.
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http://dx.doi.org/10.1021/acs.orglett.7b03155 | DOI Listing |
Chem Sci
January 2025
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology (SCUT) Guangzhou 510640 China.
Radical-mediated dearomatization strategies offer a blueprint for building value-added and synthetically valuable three-dimensional skeletons from readily available aromatic starting materials. Herein, we report a novel strategy by leveraging benzene-linked O-oxime esters as triply functionalized precursors to form two distinct persistent radicals under a chemodivergent pathway. These radicals then couple with a cyclohexadienyl radical for either carboamination or carbo-aminoalkylation.
View Article and Find Full Text PDFOrg Lett
December 2023
School of Chemistry, Dalian University of Technology, Dalian 116024, China.
Pyrroloindoline is a privileged heterocyclic motif that is widely present in many natural products and pharmaceutical compounds. Herein, we report an amidyl radical-mediated dearomatization for synthesizing a series of pyrroloindolines via N-heterocyclic carbene catalysis. In this organocatalytic process, the Breslow enolate served as both a single electron donor and an acyl radical equivalent to assemble C3a-acyl pyrroloindolines with a broad substrate scope.
View Article and Find Full Text PDFJ Org Chem
March 2022
College of Sciences, Central South University of Forestry and Technology, Changsha 410004, China.
A novel and mild metal-free catalyzed radical-mediated cascade spirocyclization of -benzylacrylamides with polyhaloalkanes is proposed for the preparation of polyhalo-substituted azaspirocyclohexadienones. Notably, polyhaloalkanes are employed as efficient alkyl radical sources via the cleavage of C(sp)-H bonds. This protocol undergoes a cascade radical addition and intramolecular cyclization/dearomatization process, and enables the easy construction of multiple chemical bonds and a spiro ring in a single reaction.
View Article and Find Full Text PDFOrg Lett
December 2017
Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Equipe Méthodologie, Synthèse et Molécules Thérapeutiques, Univ. Paris Sud, CNRS, Université Paris-Saclay, 15, rue Georges Clemenceau, 91405 Orsay, Cedex, France.
The dearomative introduction of trifluoromethyl and 1,1-difluoroethyl radicals, generated from their corresponding sulfinate salts, into the C2 position of indole derivatives allows the diastereoselective synthesis of three-dimensional 3,3-spirocyclic indolines over C-H functionalized indoles.
View Article and Find Full Text PDFOrg Biomol Chem
May 2016
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, 730000, P.R. China. and State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Lanzhou, 730000, P.R. China.
A silver-promoted oxidative cascade cyclization with a phosphorylation/1,5-aryl migration/desulfonylation/dearomatization process is presented here, providing an efficient method to synthesize azaspiro[4.5]decenones with high regioselectivity. The cinnamamidyl radical, which has rarely been reported before, plays a key role in this reaction.
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