m-Fluorobenzenethiol → HCID 59207197, compound

HRID 2242633Notes

Reaction equation

HRID 2242633 reaction equation
I[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C@H:8]([CH2:12][N:13]1[CH2:16][CH:15]([OH:17])[CH2:14]1)[CH2:7][CH2:6][CH2:5]2.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.C(N(C(C)C)CC)(C)C.[F:69][C:70]1[CH:71]=[C:72]([SH:76])[CH:73]=[CH:74][CH:75]=1>O1CCOCC1.CCOC(C)=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[NH4+:13].[OH-:17].[F:69][C:70]1[CH:71]=[C:72]([S:76][C:2]2[CH:3]=[C:4]3[C:9](=[CH:10][CH:11]=2)[C@H:8]([CH2:12][N:13]2[CH2:16][CH:15]([OH:17])[CH2:14]2)[CH2:7][CH2:6][CH2:5]3)[CH:73]=[CH:74][CH:75]=1

Participants

9

Reactant 4

HCID 75710m-FluorobenzenethiolHCID 81531DiisopropylethylamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 59207183HCID 59207183, compound

Product 2

HCID 14923Ammonium HydroxideHCID 59207197HCID 59207197, compoundYield 93.2%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

In 5 mL dioxane under argon was mixed 1-((R)-6-Iodo-1,2,3,4-tetrahydro-naphthalen-1-ylmethyl)-azetidin-3-ol (0.172 g, 0.5 mmol), tris(dibenzylideneacetone)-dipalladium(0) (0.023 g, 0.025 mmoles), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.029 g, 0.05 mmol), diisopropylethyl amine (1 mmol) and 3-fluoro-thiophenol (0.13 g, 1.0 mmoles). The reaction mixture was stirred at 60° for 45 minutes, then was cooled and diluted with EtOAc. The organic layer was washed 1.5 M aqueous sodium carbonate, dried (magnesium sulfate), filtered and concentrated under reduced pressure. The residue was subjected to preparative HPLC (hexanes/EtOAc 1:1 to 50% hexanes/27% EtOA/15% MeOH/8% con. NH4OH) to give 0.08 g (47%) of 1-[(R)-6-(3-fluoro-phenylsulfanyl)-1,2,3,4-tetrahydro-naphthalen-1-ylmethyl]-azetidin-3-ol, MS M+H=344.

Workup

  1. temperaturewas cooled
  2. washThe organic layer was washed 1.5 M aqueous sodium carbonate
  3. dry with materialdried (magnesium sulfate)
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-40f307cd39a64157a2695bfcdebc100c
Source dataset
uspto-grants-2010_03
Patent number
US07671235B2

Reaction notes

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