Ethyl Acetate → 21H,22H-Porphine

HRID 2220774Notes

Reaction equation

HRID 2220774 reaction equation
Br[C:2]1[C:3]2[NH:7][C:6]([C:8](C3C=C(C(C)(C)C)C=C(C(C)(C)C)C=3)=[C:9]3[N:40]=[C:12]([C:13](Br)=[C:14]4[NH:38][C:17](=[C:18](C5C=C(C(C)(C)C)C=C(C(C)(C)C)C=5)[C:19]5[CH:20]=[CH:21][C:22]=1[N:23]=5)[CH:16]=[CH:15]4)[CH:11]=[CH:10]3)=[CH:5][CH:4]=2.C1C=CC(P(C2C(OC3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=CC=3)=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[Cs+].[Cs+].C(OCC)(=O)C>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:3]12[CH:2]=[C:22]3[N:23]=[C:19]([CH:20]=[CH:21]3)[CH:18]=[C:17]3[NH:38][C:14]([CH:15]=[CH:16]3)=[CH:13][C:12]3=[N:40][C:9]([CH:10]=[CH:11]3)=[CH:8][C:6]([NH:7]1)=[CH:5][CH:4]=2

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 178440595HCID 178440595, compound

Product 1

HCID 13770524121H,22H-Porphine

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

The general procedure was used to couple 5,15-dibromo-10,20-di(3,5-di-tert-butylphenyl)porphyrin (0.043 g, 0.05 mmol) with (+)-dihydrocholesterol (0.1556 g, 0.4 mmol), using Pd2(dba)3 (0.0046 g, 0.005 mmol) and DPEphos (0.0107 g, 0.02 mmol) in the presence of Cs2CO3 (0.0652 g, 0.2 mmol). The reaction was conducted in toluene (5 mL) at 100° C. for 18 h. The title compound was isolated by flash column chromatography (silica gel, ethyl acetate:hexanes (v/v)=1:20) as purple solids (0.059 g, 79%). 1H NMR (300 MHz, CDCl3): δ 9.46 (d, J=4.8 Hz, 4H), 8.87 (d, J=4.8 Hz, 4H), 8.09 (d, J=2.1 Hz, 4H), 7.81 (t, J=1.8 Hz, 2H), 5.01 (m, 2H), 2.26-0.61 (m, 92H), 1.57 (s, 36H), −2.48 (s, 2H). 13C NMR (75 MHz, CDCl3): δ 148.9, 140.8, 135.8, 130.6, 129.9, 127.4, 121.0, 120.8, 91.6, 56.3, 56.1, 54.2, 44.9, 42.5, 39.9, 39.5, 37.0, 36.1, 35.8, 35.7, 35.4, 35.0, 31.8, 29.3, 28.7, 28.2, 28.0, 24.1, 23.8, 22.8, 22.5, 21.9, 18.6, 12.6, 12.0. UV-vis (CHCl3, λmax, nm): 420, 521, 560, 604, 661. HRMS-MALDI ([M+H]+): calcd for C102H147N4O2, 1460.1519, found 1460.1522 with an isotope distribution pattern that is the same as calculated one.

Sources & evidence

ORD record
ord-e06ba5dba30a4cc4b9426fb74e279e7e
Source dataset
uspto-grants-2008_08
Patent number
US07417142B2

Reaction notes

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