DOI: 10.5061/dryad.mpg4f4rcj
title: 1,4-Reduction of α,β-unsaturated ketones catalyzed by tetraarylhydrophosphoranes

description: We demonstrate that a pentavalent phosphorous compound,
 tetraarylhydrophosphorane, is capable of catalyzing 1,4-reduction of
 α,β-unsaturated ketones in the presence of pinacolborane. The structure
 and properties of tetraarylhydrophosphorane and its participation in the
 chemoselective 1,4-reduction were elucidated through both experimental and
 theoretical approaches.
description: They are collected through data acquisition on the NMR
 spectrometers.
description: # README: 1,4-Reduction of α,β-Unsaturated Ketones Catalyzed by
 Tetraarylhydrophosphoranes ## Description of the data and file structure
 The uploaded zip file contains primary nuclear magnetic resonance (NMR)
 files for compounds **P2**, **PH2**, **1b**-**1w**, **1y**, **2a**-**2y**,
 **3a**, **4a**, **5a**, and **5a’**
 ([https://pubs.acs.org/doi/10.1021/acs.orglett.5c02773](https://pubs.acs.org/doi/10.1021/acs.orglett.5c02773)). These compounds are classified into the “Catalyst”, “StartingMaterial”, and "Product" folders. The detailed contents of each folder are provided in the section below. Each compound folder contains ¹H NMR and ¹³C NMR data; for some compounds, ¹⁹F NMR and ³¹P NMR data are also included. The filenames follow the format “CompoundName_Nuclear.” The NMR data are stored in one of the following formats: • “.jdf” (JEOL NMR instrument) • A single folder containing “fid” (the main data file) and auxiliary files (Bruker NMR instrument) To view the NMR spectrum, you need to give the ".jdf" file or the entire folder of files (e.g. FIDdata/StartingMaterial/1b/1b_H/) to the software (see "Code/Software" section). The software will use the fid file inside the file/folder and the associated files to generate the spectrum. ### The full name of the compounds represented by the compound number *Catalyst folder* **P2**: 5,5-Diphenyl-5*H*-benzo[*b*]phosphindol-5-ium trifluoromethanesulfonate **PH2**: (2,2’-Biphenylylene)diphenylhydrophosphorane *StartingMaterial folder* **1b**: (*E*)-3-(4-Methoxyphenyl)-1-phenylprop-2-en-1-one **1c**: (*E*)-3-(4-(Cyclopropylmethoxy)phenyl)-1-phenylprop-2-en-1-one **1d**: (*E*)-3-(4-Bromophenyl)-1-phenylprop-2-en-1-one **1e**: (*E*)-1-Phenyl-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one **1f**: (*E*)-3-(2,6-Difluorophenyl)-1-phenylprop-2-en-1-one **1g**: (*E*)-4-(3-Oxo-3-phenylprop-1-en-1-yl)benzonitrile **1h**: (*E*)-3-(4-Nitrophenyl)-1-phenylprop-2-en-1-one **1i**: (*E*)-3-(4-Acetylphenyl)-1-phenylprop-2-en-1-one **1j**: Methyl (*E*)-4-(3-oxo-3-phenylprop-1-en-1-yl)benzoate **1k**: (*E*)-3-(4-(Pent-1-yn-1-yl)phenyl)-1-phenylprop-2-en-1-one **1l**: (*E*)-3-(Naphthalen-2-yl)-1-phenylprop-2-en-1-one **1m**: (*E*)-1-Phenyl-3-(1-tosyl-1*H*-indol-5-yl)prop-2-en-1-one **1n**: (*E*)-3-Ferrocenyl-1-phenylprop-2-en-1-one **1o**: (*E*)-1-(4-Iodophenyl)-3-phenylprop-2-en-1-one **1p**: (*E*)-1-(Benzo[*d*][1,3]dioxol-5-yl)-3-phenylprop-2-en-1-one **1q**: (*E*)-1-(2,4-Dimethoxyphenyl)-3-(4-methoxyphenyl)propan-1-one **1r**: (*E*)-3-Phenyl-1-(Thiophen-3-yl)prop-2-en-1-one **1s**: (2*E*,2’*E*)-3,3’-(1,4-Phenylene)bis(1-phenylprop-2-en-1-one) **1t**: (*E*)-1-Phenylhex-2-en-1-one **1u**: (*E*)-4,4,4-Trifluoro-1-phenylbut-2-en-1-one **1v**: (*E*)-4,4-Dimethyl-1-phenylpent-1-en-3-one **1w**: (*E*)-1-Phenyloct-4-en-3-one **1y**: (*E*)-1,7-Diphenylhept-2-ene-1,7-dione *Product folder* **2a**: 1,3-Diphenylpropan-1-one **2b**: 3-(4-Methoxyphenyl)-1-phenylpropan-1-one **2c**: 3-(4-(Cyclopropylmethoxy)phenyl)-1-phenylpropan-1-one **2d**: 3-(4-Bromophenyl)-1-phenylpropan-1-one **2e**: 1-Phenyl-3-(4-(trifluoromethyl)phenyl)propan-1-one **2f**: 3-(2,6-Difluorophenyl)-1-phenylpropan-1-one **2g**: 4-(3-Oxo-3-phenylpropyl)benzonitrile **2h**: 3-(4-Nitrophenyl)-1-phenylpropan-1-one **2i**: 3-(4-Acetylphenyl)-1-phenylpropan-1-one **2j**: Methyl 4-(3-oxo-3-phenylpropyl)benzoate **2k**: 3-(4-(Pent-1-yn-1-yl)phenyl)-1-phenylpropan-1-one **2l**: 3-(Naphthalen-2-yl)-1-phenylpropan-1-one **2m**: 1-Phenyl-3-(1-tosyl-1*H*-indol-3-yl)propan-1-one **2n**: 3-Ferrocenyl-1-phenylpropan-1-one **2o**: 1-(4-Iodophenyl)-3-phenylpropan-1-one **2p**: 1-(Benzo[*d*][1,3]dioxol-5-yl)-3-phenylpropan-1-one **2q**: 1-(2,4-Dimethoxyphenyl)-3-(4-methoxyphenyl)propan-1-one **2r**: 3-Phenyl-1-(thiophen-3-yl)propan-1-one **2s**: 3,3'-(1,4-Phenylene)bis(1-phenylpropan-1-one) **2t**: 1-Phenylhexan-1-one **2u**: 4,4,4-Trifluoro-1-phenylbutan-1-one **2v**: 4,4-Dimethyl-1-phenylpentan-3-one **2w**: 1-Phenyloctan-3-one **2x**: 2-Pentylcyclopentan-1-one **2y**: ((1*R**,2*S**)-2-Hydroxy-2-phenylcyclohexyl)(phenyl)methanone **3a**: (*E*)-1,3-Diphenylprop-2-en-1-ol **4a**: 2-Benzyl-2-bromoacetophenone **5a**: (2*R*,3*S*)-2-Benzyl-3-cyclohexyl-3-hydroxy-1-phenylpropan-1-one **5a'**: (2*R*,3*R*)-2-Benzyl-3-cyclohexyl-3-hydroxy-1-phenylpropan-1-one ## Sharing/Access information Compound structures and their NMR data are available as images in the [Supporting Information](https://pubs.acs.org/doi/10.1021/acs.orglett.5c02773). ## Code/Software NMR data can be processed by various softwares, such as NMRium ([https://app.nmrium.com/](https://app.nmrium.com/)), MestReNova ([https://mestrelab.com/software/mnova/](https://mestrelab.com/software/mnova/)), iNMR (free demo can display FID data) ([https://www.inmr.net/](https://www.inmr.net/)), and JEOL Delta ([https://www.jeol.com/products/scientific/nmr_software/Delta5.php](https://www.jeol.com/products/scientific/nmr_software/Delta5.php)).