Estrone → HCID 136375620, compound

HRID 2220781Notes

Reaction equation

HRID 2220781 reaction equation
Br[C:2]1[C:3]2[NH:7][C:6]([C:8]([C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)=[C:9]3[N:31]=[C:12]([CH:13]=[C:14]4[NH:30][C:17](=[C:18]([C:24]5[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=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.[CH3:38][C@@:39]12[C:55](=[O:56])[CH2:54][CH2:53][C@H:52]1[C@H:51]1[C@@H:42]([C:43]3[CH:44]=[CH:45][C:46]([OH:57])=[CH:47][C:48]=3[CH2:49][CH2:50]1)[CH2:41][CH2:40]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+]>C1COCC1.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(Cl)Cl>[C:24]1([C:18]2[C:19]3[CH:20]=[CH:21][C:22]([N:23]=3)=[C:2]([O:57][C:46]3[CH:45]=[CH:44][C:43]4[CH:42]5[CH:51]([CH2:50][CH2:49][C:48]=4[CH:47]=3)[CH:52]3[C:39]([CH3:38])([C:55](=[O:56])[CH2:54][CH2:53]3)[CH2:40][CH2:41]5)[C:3]3[NH:7][C:6]([C:8]([C:32]4[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=4)=[C:9]4[N:31]=[C:12]([CH:13]=[C:14]5[NH:30][C:17]=2[CH:16]=[CH:15]5)[CH:11]=[CH:10]4)=[CH:5][CH:4]=3)[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1

Participants

8

Reactant 4

HCID 5870EstroneHCID 10796Cesium carbonateHCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 173154257HCID 173154257, compound

Product 1

HCID 136375620HCID 136375620, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

The general procedure was used to couple 5-bromo-10,20-diphenylporphin (27.1 mg, 0.05 mmol) with estrone (27 mg, 0.1 mmol), using Pd2(dba)3 (2.3 mg, 0.0025 mmol) and DPEphos (5.38 mg, 0.01 mmol) in the presence of Cs2CO3 (37.6 mg, 0.1 mmol). The reaction was conducted in THF at 100° C. for 24 h. The title compound was isolated by flash chromatography (silica gel, methylene chloride: hexanes (v/v)=8:2) as a purple-red solid (20 mg, 55%). 1H NMR (300 MHz, CDCl3) δ 10.13 (s, 1H), 9.39 (d, J=4.8 Hz, 2H), 9.29 (d, J=4.8 Hz, 4H), 8.98 (d, J=4.8 Hz, 4H), 8.86 (d, J=4.8 Hz, 4H), 8.22 (m, 4H), 7.75 (m, 6H), 7.14 (d, J=9.0 Hz, 1H), 6.88 (d, J=8.4 Hz, 1H), 6.64 (d, J=1.8 Hz, 1H), 1.86-2.62 (m, H from estrone), 1.26-1.52 (m, H from estrone), 0.85 (s, 3H), −2.77 (s, 2H). 13C NMR (75 MHz, CDCl3): δ 141.2, 138.1, 134.7, 133.0, 131.5, 130.8, 127.9, 127.8, 126.9, 126.5, 120.2, 119.7, 116.6, 114.1, 104.6, 50.3, 47.9, 44.0, 38.1, 35.8, 31.5, 29.4, 26.3, 25.8, 21.5, 13.8. UV-vis (CH2Cl2, Amax, nm): 413, 510, 544, 585, 641. HRMS-EI ([M]+): calcd for C50H42N4O2, 730.3308, found 730.3294.

Sources & evidence

ORD record
ord-1aaa5d25a2294dec8ec823925b704d60
Source dataset
uspto-grants-2008_08
Patent number
US07417142B2

Reaction notes

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