Thiophenol → HCID 90409908, compound

HRID 1855076Notes

Reaction equation

HRID 1855076 reaction equation
FC(F)(F)S(O[C:7]1[CH:8]=[C:9]([C:13]23[CH2:20][CH2:19][C:16]([CH2:21][CH2:22][O:23][CH2:24][C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])([CH2:17][CH2:18]2)[CH2:15][O:14]3)[CH:10]=[CH:11][CH:12]=1)(=O)=O.[C:34]1([SH:40])[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.CCN(C(C)C)C(C)C>O1CCOCC1.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]>[C:34]1([S:40][C:7]2[CH:8]=[C:9]([C:13]34[CH2:20][CH2:19][C:16]([CH2:21][CH2:22][O:23][CH2:24][C:25]([O:27][C:28]([CH3:30])([CH3:31])[CH3:29])=[O:26])([CH2:17][CH2:18]3)[CH2:15][O:14]4)[CH:10]=[CH:11][CH:12]=2)[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1

Participants

7

Reactant 4

HCID 7969ThiophenolHCID 81531DiisopropylethylamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 90409180HCID 90409180, compound

Product 1

HCID 90409908HCID 90409908, compoundYield 95.1%

Reagents, catalysts & solvents 2

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

Procedure

A solution of tert-butyl 2-(2-(1-(3-(((trifluoromethyl)sulfonyl)oxy)phenyl)-2-oxabicyclo[2.2.2]octan-4-yl)ethoxy)acetate (80 mg, 0.162 mmol), thiophenol (0.025 mL, 0.243 mmol), XantPhos (18.72 mg, 0.032 mmol), and Pd2(dba)3 (14.8 mg, 0.016 mmol) in 1,4-dioxane (1 mL) was degassed with low vacuum under Ar five times using a sonicator. DIPEA (0.085 mL, 0.485 mmol) pre-degassed in the same way was added under an atmosphere of Ar. The mixture was heated to reflux for 2 h, then was cooled to rt, filtered, and the filtrate was concentrated in vacuo. The crude oil was chromatographed (SiO2) using a gradient from 0% to 50% EtOAc/hexane (10 min) to give the title compound (70 mg, 0.154 mmol, 95% yield) as a clear oil. LCMS: [M+Na]+=477.1. 1H NMR (CDCl3) δ: 7.48 (t, J=1.8 Hz, 1H), 7.35-7.27 (m, 6H), 7.26-7.18 (m, 2H), 3.96 (s, 2H), 3.88 (s, 2H), 3.58 (t, J=6.9 Hz, 2H), 2.06-1.97 (m, 4H), 1.73 (dd, J=9.1, 6.8 Hz, 4H), 1.51 (s, 11H).

Workup

  1. additionwas added under an atmosphere of Ar
  2. temperatureThe mixture was heated
  3. temperatureto reflux for 2 h
  4. filtrationfiltered
  5. concentrationthe filtrate was concentrated in vacuo
  6. customThe crude oil was chromatographed (SiO2)
  7. customfrom 0% to 50% EtOAc/hexane (10 min)

Sources & evidence

ORD record
ord-8b0c44583d3e402ab4a4b92b31539bc7
Source dataset
uspto-grants-2015_02
Patent number
US08962660B2

Reaction notes

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