Triphenylphosphine → HCID 86612918, compound

HRID 2422360Notes

Reaction equation

HRID 2422360 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C.[F:34][C:35]([F:46])([F:45])[C:36]([NH:38][C:39]1[CH:43]=[CH:42][S:41][C:40]=1[I:44])=[O:37].[C:47]([O:51][C:52]([N:54]1[CH2:59][CH:58]=[C:57]([CH2:60]O)[CH2:56][CH2:55]1)=[O:53])([CH3:50])([CH3:49])[CH3:48]>O1CCCC1>[C:47]([O:51][C:52]([N:54]1[CH2:55][CH:56]=[C:57]([CH2:60][N:38]([C:39]2[CH:43]=[CH:42][S:41][C:40]=2[I:44])[C:36](=[O:37])[C:35]([F:34])([F:45])[F:46])[CH2:58][CH2:59]1)=[O:53])([CH3:50])([CH3:48])[CH3:49]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 225944841,1-Dimethylethyl 3,6-dihydro-4-(hydroxymethyl)-1(2H)-pyridinecarboxylateHCID 588961652,2,2-Trifluoro-N-(2-iodothiophen-3-yl)acetamide

Product 1

HCID 86612918HCID 86612918, compoundYield 62.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-10 °C

Procedure

Triphenylphosphine (2.29 g) was dissolved in tetrahydrofuran (50 ml) and the solution was cooled to −10° C. under argon. Diisopropylazodicarboxylate (1.70 ml) was added dropwise over 10 min and the resulting mixture was stirred at −10° C. for 20 min (formation of a white precipitate). 2,2,2-Trifluoro-N-(2-iodo-thiophen-3-yl)-acetamide (2.25 g) dissolved in a minimum volume of tetrahydrofuran was added, followed by 4-Hydroxymethyl-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (J. Org. Chem. 2001, 66, 5545-5551, 1.49 g) dissolved in a minimum volume of tetrahydrofuran. The reaction mixture was allowed to warm to room temperature and stirred for 12 hours. The solution was then concentrated in vacuo and the residue subjected to silica gel chromatography (cyclohexane:ethyl acetate 93:7) to afford 4-{[(2-Iodo-thiophen-3-yl)-(2,2,2-trifluoro-acetyl)-amino]-methyl}-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester as a colourless oil (2.27 g). 1H NMR (400 MHz, CDCl3) 1.5 (s, 9H), 2.15 (m, 2H), 3.43 (m, 1H), 3.52 (m 1H), 3.75 (d, J=19 Hz, 1H), 3.77 (m, 2H), 4.76 (d, J=17 Hz, 1H), 5.41 (s, 1H), 6.68 (br d, J=5.5 Hz, 1H), 7.42 (d, J=5.5 Hz, 1H); MS (ES+) 417 (M+H+—CO2-isobutene), 458 (M+H+-isobutene).

Workup

  1. additionwas added
  2. temperatureto warm to room temperature
  3. stirringstirred for 12 hours
  4. concentrationThe solution was then concentrated in vacuo

Sources & evidence

ORD record
ord-09faa6974126477da963b80ca1b4448f
Source dataset
uspto-grants-2011_06
Patent number
US07960401B2

Reaction notes

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