DOI: 10.5061/dryad.3tx95x6sq
title: Photocatalyzed/base-mediated defluorinative three-component cascade cyclization: Access to monofluorocyclohexenes and 6-fluoro-1,2,3,4-tetrahydropyridines

description: A three-component cascade cyclization of α-CF3 alkenes, electron-rich
 alkenes, and dimethyl esters or sulfonamides via a dual C-F bond cleavage
 process is described. This methodology provides a general and efficient
 strategy to access monofluorocyclohexenes and
 6-fluoro-1,2,3,4-tetrahydropyridines by switching the bifunctional
 reagents (dimethyl esters or sulfonamides), which are valuable building
 blocks in synthetic chemistry and the pharmaceutical industries. The
 reaction mechanism and the synthetic applications of the products have
 been demonstrated.
description: # Photocatalyzed/base-mediated defluorinative three-component cascade
 cyclization: Access to monofluorocyclohexenes and
 6-fluoro-1,2,3,4-tetrahydropyridines 1H NMR, 19F NMR, 13C NMR spectra, and
 high-resolution mass spectra (HRMS) in the Spectra.zip file are used to
 describe the structure and the exact molecular mass of 46 new compounds in
 the publication: Photocatalyzed/base-mediated defluorinative
 three-component cascade cyclization: Access to monofluorocyclohexenes and
 6-fluoro-1,2,3,4-tetrahydropyridines. (DOI:10.1021/acs.orglett.5c00675) ##
 Description of the data and file structure Spectra.zip includes FID for
 Publication.zip and a folder named HRMS for Publication. The documents are
 classified and named for the compound number designated in the manuscript
 and SI, and by 1H, 13C, or 19F for 1H NMR, 13C NMR, or 19F NMR,
 respectively. **Abbreviations used are as follows:** NMR: nuclear magnetic
 resonance SI: supporting information (meaning, Supplementary Materials
 document) HRMS: high-resolution mass spectra ### The full name of the
 compounds represented by the compound number **4a**: dimethyl
 2-(4-([1,1'-biphenyl]-4-yl)-2-butoxy-5,5-difluoropent-4-en-1-yl)
 malonate **5a**: dimethyl
 5-butoxy-2-fluoro-5,6-dihydro-[1,1':4',1''-terphenyl]-3,3(4*H*)-dicarboxylate **5b**: dimethyl 5-butoxy-2-fluoro-5,6-dihydro-[1,1'-biphenyl]-3,3(4*H*)-dicarboxylate **5c**: dimethyl 5-butoxy-2-fluoro-4'-methyl-5,6-dihydro-[1,1'-biphenyl]-3,3(4*H*)-dicarboxylate **5d**: dimethyl 5-butoxy-4'-(tert-butyl)-2-fluoro-5,6-dihydro-[1,1'-biphenyl]-3,3(4*H*)-dicarboxylate **5e**: dimethyl 5-butoxy-2-fluoro-4'-methoxy-5,6-dihydro-[1,1'-biphenyl]-3,3(4*H*)-dicarboxylate **5f**: dimethyl 5-butoxy-4'-chloro-2-fluoro-5,6-dihydro-[1,1'-biphenyl]-3,3(4*H*)-dicarboxylate **5g**: dimethyl 5-butoxy-4'-cyano-2-fluoro-5,6-dihydro-[1,1'-biphenyl]-3,3(4*H*)-dicarboxylate **5h**: trimethyl 5-butoxy-2-fluoro-5,6-dihydro-[1,1'-biphenyl]-3,3,4'(4*H*)-tricarboxylate **5i**: dimethyl 5-butoxy-2-fluoro-3'-methyl-5,6-dihydro-[1,1'-biphenyl]-3,3(4*H*)-dicarboxylate **5j**: dimethyl 5-butoxy-2-fluoro-3-(naphthalen-1-yl)cyclohex-2-ene-1,1-dicarboxylate **5k**: dimethyl 5-butoxy-2-fluoro-3-(naphthalen-2-yl)cyclohex-2-ene-1,1-dicarboxylate **5l**: dimethyl 5-butoxy-2-fluoro-3-(quinolin-3-yl)cyclohex-2-ene-1,1-dicarboxylate **5m**: dimethyl 5-acetoxy-2-fluoro-5,6-dihydro-[1,1':4',1''-terphenyl]-3,3(4*H*)-dicarboxylate **5n**: dimethyl 2-fluoro-5-(2-oxopyrrolidin-1-yl)-5,6-dihydro-[1,1':4',1''-terphenyl]-3,3(4H)-dicarboxylate **5o**: dimethyl 5-butyl-2-fluoro-5,6-dihydro-[1,1':4',1''-terphenyl]-3,3(4*H*)-dicarboxylate **5p**: dimethyl 5-benzyl-2-fluoro-5,6-dihydro-[1,1':4',1''-terphenyl]-3,3(4*H*)-dicarboxylate **5q**: dimethyl 5-((1,3-dioxoisoindolin-2-yl)methyl)-2-fluoro-5,6-dihydro-[1,1':4',1''-terphenyl]-3,3(4*H*)-dicarboxylate **5r**: dimethyl 5-acetoxy-2-fluoro-5-methyl-5,6-dihydro-[1,1':4',1''-terphenyl]-3,3(4*H*)-dicarboxylate **5s**: 9-ethyl 2,2-dimethyl 4-([1,1'-biphenyl]-4-yl)-3-fluorospiro[5.5]undec-3-ene-2,2,9-tricarboxylate **5t**: dimethyl 6-([1,1'-biphenyl]-4-yl)-5-fluoro-1,2,3,3a,7,7a-hexahydro-4H-indene-4,4-dicarboxylate **5u**: dimethyl 6-([1,1'-biphenyl]-4-yl)-5-fluoro-3,3a,7,7a-tetrahydrobenzofuran-4,4(2H)-dicarboxylate **5v**: dimethyl 7-([1,1'-biphenyl]-4-yl)-6-fluoro-2,3,4,4a,8,8a-hexahydro-5H-chromene-5,5-dicarboxylate **5w**: methyl (7aR)-5-([1,1'-biphenyl]-4-yl)-4-fluoro-7,7-dimethyl-3-oxo-1,6,7,7a-tetrahydroisobenzofuran-3a(3H)-carboxylate **7a**: 5-([1,1'-biphenyl]-4-yl)-3-butoxy-6-fluoro-1-tosyl-1,2,3,4-tetrahydropyridine **7b**: 3-butoxy-6-fluoro-5-(4-methoxyphenyl)-1-tosyl-1,2,3,4-tetrahydropyridine **7c**: methyl-4-(5-butoxy-2-fluoro-1-tosyl-1,4,5,6-tetrahydropyridin-3-yl)benzoate **7d**: 3-butoxy-5-(3-chlorophenyl)-6-fluoro-1-tosyl-1,2,3,4-tetrahydropyridine **7e**: 5-([1,1'-biphenyl]-2-yl)-3-butoxy-6-fluoro-1-tosyl-1,2,3,4-tetrahydropyridine **7f**: 5-(benzo[b]thiophen-3-yl)-3-butoxy-6-fluoro-1-tosyl-1,2,3,4-tetrahydropyridine **7g**: 3-(5-butoxy-2-fluoro-1-tosyl-1,4,5,6-tetrahydropyridin-3-yl)quinoline **7h**: 5-([1,1'-biphenyl]-4-yl)-3-(benzyloxy)-6-fluoro-1-tosyl-1,2,3,4-tetrahydropyridine **7i**: methyl 4-([1,1'-biphenyl]-4-yl)-3-fluoro-2-tosyl-2-azaspiro[5.5]undec-3-ene-9-carboxylate **7j**: 5-([1,1'-biphenyl]-4-yl)-6-fluoro-3-methoxy-3-methyl-1-tosyl-1,2,3,4-tetrahydropyridine **7k**: 5-([1,1'-biphenyl]-4-yl)-6-fluoro-3-methyl-3-phenoxy-1-tosyl-1,2,3,4-tetrahydropyridine **7l**: 5-([1,1'-biphenyl]-4-yl)-3-(((10S,13S,14R)-10,13-dimethyl-16-((S)-6-methylheptan-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl)oxy)-6-fluoro-1-tosyl-1,2,3,4-tetrahydropyridine **7m**: 5-([1,1'-biphenyl]-4-yl)-3-(((3aR,5S,6S,6aR)-5-((S)-4,4-dimethyl-1,3-dioxolan-2yl)-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-yl)oxy)-6-fluoro-1-tosyl-1,2,3,4-tetrahydropyridine **7n**: 5-([1,1'-biphenyl]-4-yl)-3-butoxy-6-fluoro-1-(phenylsulfonyl)-1,2,3,4-tetrahydropyridine **7o**: 5-([1,1'-biphenyl]-4-yl)-3-butoxy-6-fluoro-1-(methylsulfonyl)-1,2,3,4-tetrahydropyridine **7p**: 5-([1,1'-biphenyl]-4-yl)-3-butoxy-1-(cyclopropylsulfonyl)-6-fluoro-1,2,3,4-tetrahydropyridine **8**: methyl 5-butoxy-2-fluoro-3,4,5,6-tetrahydro-[1,1':4',1''-terphenyl]-3-carboxylate **9**: 8-([1,1'-biphenyl]-4-yl)-10-butoxy-7-fluoro-2,4-diazaspiro[5.5]undec-7-ene-1,3,5-trione **10**: 8-([1,1'-biphenyl]-4-yl)-10-butoxy-7-fluoro-3,3-dimethyl-2,4-dioxaspiro[5.5]undec-7-ene **11**: 5-([1,1'-biphenyl]-4-yl)-3-butoxy-6-methoxy-2,3,4,5-tetrahydropyridine **12**: 3-([1,1'-biphenyl]-4-yl)-5-butoxypyridine 4-methylbenzenesulfonate **13**: dimethyl 2-((2-(2-([1,1'-biphenyl]-4-yl)-3,3-difluoroallyl)-6,6-dimethylbicyclo[3.1.1]heptan-2-yl)methyl)malonate ### FID for Publication.zip Includes 1H NMR, 19F NMR, 13C NMR spectra fid documents of compounds **4a, 5a-5w, 7a-7p, 8-13**. The data files are packaged into folders for each compound characterized in the manuscript. The data are structured in folders for each NMR spectrum. Each folder contains the fid files and all acquisition and processing parameters used while obtaining the NMR spectrum. The folder should provide all information necessary to open the data and display the NMR spectrum in the NMR processing software. Mestrenova. Accessing this data will allow users to view NMR spectra interactively. ### HRMS for Publication folder Includes .png and .pdf documents of high-resolution mass spectra test figures of compounds **4a**,**5a-5w**, **7a-7p**,**8-13**. The exact molecular mass of each compound can be found in the figure. ## Sharing/access Information NMR data will be available as images, and HRMS data will be provided as the extracted mass values in the SI for this manuscript.