Cesium carbonate → 21H,22H-Porphine

HRID 2220777Notes

Reaction equation

HRID 2220777 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@@H]1COC(=O)N1)C1C=CC=CC=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.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(OCC)(=O)C.C(Cl)Cl>[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

9

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 2734969(R)-4-Benzyl-2-oxazolidinoneHCID 178419281HCID 178419281, compound

Product 1

HCID 13770524121H,22H-Porphine

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

The general procedure described by Gao et al., (2004) Org. Lett., 6:1837, was used to couple 5,15-dibromo-10,20-diphenylporphyrin (31.0 mg, 0.05 mmol) with (R)-(+)-4-benzyl-2-oxazolidinone (70.8 mg, 0.4 mmol), using Pd2(dba)3 (2.3 mg, 0.0025 mmol) and Xantphos (5.78 mg, 0.01 mmol) in the presence of Cs2CO3 (65.2 mg, 0.2 mmol). The reaction was conducted in THF at 68° C. for 22 h., The title compound was isolated by flash chromatography (silica gel, methylene chloride:ethyl acetate (v/v)=9:1) as a purple mixture of two atropic isomers (25 mg, 62%, α,α/α,β=50%/50%). 1H NMR (300 MHz, CDCl3): δ 9.46 (d, J=5.1 Hz, 4H), 9.42 (d, J=4.8 Hz, 4H), 9.24 (t, J=4.2 Hz, 4H), 9.00 (d, J=4.8 Hz, 2H), 8.96 (d, J=4.2 Hz, 4H), 8.93 (d, J=4.8 Hz, 2H), 8.32 (d, J=4.8 Hz, 2H), 8.20 (t, J=7.2 Hz, 4H), 8.06 (d, J=4.8 Hz, 2H), 7.79 (m, 12H), 7.07 (m, 6H), 7.02 (m, 6H), 6.83 (m, 8H), 5.35 (m, 2H), 5.23 (m, 2H), 5.00 (dd, J=9.0 Hz, 4H), 4.82 (dd, J=9.0 Hz, 4H), 3.13-3.30 (m, 4H), 2.94 (dd, J=13.2, 3.3 Hz, 2H), 2.70 (dd, J=13.2, 3.3 Hz, 2H), −2.84 (s, 2H), −2.89 (s, 2H); 13C NMR (75 MHz, CDCl3): δ 147.1, 140.1, 140.9, 135.0, 134.6, 128.8, 128.7, 128.2, 127.1, 126.9, 126.8, 121.4, 111.5, 68.3, 66.4, 40.4, 40.3. UV-vis (CH2Cl2, λmax, nm): 412, 526, 558. HRMS-MALDI ([M+H]+): calcd for C52H41N6O4, 813.3184, found 813.3194 with an isotope distribution pattern that is the same as calculated one.

Sources & evidence

ORD record
ord-f79971902bb64bdd81a8564c9f38ff51
Source dataset
uspto-grants-2008_08
Patent number
US07417142B2

Reaction notes

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