Triethylamine → Methyl 1-benzyl-4-formyl-5-(3-hydroxy-3,3-diphenylprop-1-ynyl)-1H-pyrrole-2-carboxylate

HRID 1952523Notes

Reaction equation

HRID 1952523 reaction equation
[CH2:1]([N:8]1[C:12](I)=[C:11]([CH:14]=[O:15])[CH:10]=[C:9]1[C:16]([O:18][CH3:19])=[O:17])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:20]1([C:26]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)([OH:29])[C:27]#[CH:28])[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCN(CC)CC>CN(C=O)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:1]([N:8]1[C:12]([C:28]#[C:27][C:26]([OH:29])([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)=[C:11]([CH:14]=[O:15])[CH:10]=[C:9]1[C:16]([O:18][CH3:19])=[O:17])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 92976DiphenylethynylcarbinolHCID 86664847Methyl 1-benzyl-4-formyl-5-iodo-1H-pyrrole-2-carboxylate

Product 1

HCID 86664849Methyl 1-benzyl-4-formyl-5-(3-hydroxy-3,3-diphenylprop-1-ynyl)-1H-pyrrole-2-carboxylateYield 87%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Procedure

A solution of 5 (0.47 g, 1.3 mmol), 1,1-diphenylprop-2-yn-1-ol (0.66 g, 3.2 mmol), CuI (0.05 g, 0.3 mmol), Pd(PPh3)2Cl2 (0.18 g, 0.3 mmol), PPh3 (0.07 g, 0.3 mmol), and Et3N (4 mL) in anhydrous DMF (4 mL) was stirred for 16 hours at 70° C. under N2 atmosphere. The reaction mixture was partitioned between water and EtOAc. The combined organic layer was dried over MgSO4, filtered and concentrated in vacuo. MPLC purification (Hexanes:EtOAc/80:20) of the residue gave 6 as a pale yellow solid (0.49 g, 87%). 1H NMR (400 MHz, CDCl3) δ 9.88 (s, 1H), 7.50-7.52 (m, 4H), 7.36 (s, 1H), 7.24-7.30 (m, 8H), 7.04 (m, 2H), 5.69 (s, 2H), 3.80 (s, 3H), and 3.65 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 185.16, 160.72, 144.07, 136.84, 128.91, 128.72, 128.33, 127.91, 127.79, 127.05, 126.23, 124.96, 116.97, 103.35, 75.37, 75.27, 52.15, and 50.38.

Workup

  1. customThe reaction mixture was partitioned between water and EtOAc
  2. dry with materialThe combined organic layer was dried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customMPLC purification (Hexanes:EtOAc/80:20) of the residue

Sources & evidence

ORD record
ord-3ba1cc3c9bcf42dfa2b3a444e23b6d8c
Source dataset
uspto-grants-2013_03
Patent number
US08404728B2

Reaction notes

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