Estrone → 21H,22H-Porphine

HRID 2220775Notes

Reaction equation

HRID 2220775 reaction equation
Br[C:2]1[C:3]2[NH:7][C:6]([C:8](C3C=CC=CC=3)=[C:9]3[N:32]=[C:12]([C:13](Br)=[C:14]4[NH:30][C:17](=[C:18](C5C=CC=CC=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.C[C@@]12C(=O)CC[C@H]1[C@@H]1CCC3C=C(O)C=CC=3[C@H]1CC2.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+]>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(OCC)(=O)C>[C:3]12[CH:2]=[C:22]3[N:23]=[C:19]([CH:20]=[CH:21]3)[CH:18]=[C:17]3[NH:30][C:14]([CH:15]=[CH:16]3)=[CH:13][C:12]3=[N:32][C:9]([CH:10]=[CH:11]3)=[CH:8][C:6]([NH:7]1)=[CH:5][CH:4]=2

Participants

8

Reactant 4

HCID 5870EstroneHCID 10796Cesium carbonateHCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 178419281HCID 178419281, compound

Product 1

HCID 13770524121H,22H-Porphine

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

The general procedure was used to couple 5,15-dibromo-10,20-diphenylporphyrin (31.0 mg, 0.05 mmol) with (+)-estrone (108 mg, 0.2 mmol), using Pd2(dba)3 (4.6 mg, 0.005 mmol) and DPEphos (10.7 mg, 0.02 mmol) in the presence of Cs2CO3 (65.2 mg, 0.2 mmol). The reaction was conducted in toluene at 100° C. for 40 h. The title compound was isolated by flash chromatography (silica gel, methylene choloride:ethyl acetate (v/v)=9:1) as a purple solid (49.1 mg, 98%). 1H NMR (300 MHz, CDCl3): δ 9.30 (d, J=4.5 Hz, 4H), 8.78 (d, J=4.8 Hz, 4H), 8.16 (m, 4H), 7.74 (m, 6H), 7.16 (d, J=8.4 Hz, 1H), 7.13 (d, J=8.4 Hz, 1H), 6.89 (d, J=8.4, 2.7 Hz, 1H), 6.86 (d, J=8.4, 3.0 Hz, 1H), 6.65 (d, J=3.0 Hz, 2H), 1.20-2.8 (m, 30H), 0.88 (s, 3H), 0.86 (s, 3H), −2.47 (s, 2H). 13C NMR (75 MHz, CDCl3): δ 141.1, 138.1, 134.6, 133.1, 132.0, 131.3, 131.0, 127.8, 126.9, 120.2, 116.3, 114.0, 50.3, 47.9, 44.0, 38.3, 38.1, 35.9, 31.5, 29.4, 26.3, 25.8, 21.5, 13.8. UV-vis (CH2Cl2, λmax, nm): 420, 517, 555, 598, 655. HRMS-EI ([M]+): calcd for C68H62N4O4, 998.4771, found 998.4773 with an isotope distribution pattern that is the same as calculated one.

Sources & evidence

ORD record
ord-47b106b2aa4d464684882c84b7280fe9
Source dataset
uspto-grants-2008_08
Patent number
US07417142B2

Reaction notes

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