Cesium carbonate → 21H,22H-Porphine

HRID 2220778Notes

Reaction equation

HRID 2220778 reaction equation
Br[C:2]1[C:3]2[NH:7][C:6]([C:8](C3C(C)=CC(C)=CC=3C)=[C:9]3[N:35]=[C:12]([C:13](Br)=[C:14]4[NH:33][C:17](=[C:18](C5C(C)=CC(C)=CC=5C)[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:3]12[CH:2]=[C:22]3[N:23]=[C:19]([CH:20]=[CH:21]3)[CH:18]=[C:17]3[NH:33][C:14]([CH:15]=[CH:16]3)=[CH:13][C:12]3=[N:35][C:9]([CH:10]=[CH:11]3)=[CH:8][C:6]([NH:7]1)=[CH:5][CH:4]=2

Participants

8

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 178424430HCID 178424430, compound

Product 1

HCID 13770524121H,22H-Porphine

Reagents, catalysts & solvents 3

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

Procedure

The general procedure was used to couple 5,15-dibromo-10,20-di(2′,4′,6′-trimethylphenyl)porphyrin (0.035 g, 0.05 mmol) with (R)-(+)4-benzyl-2-oxazolidinone (0.0708 g, 0.4 mmol), using Pd2(dba)3 (0.0046 g, 0.005 mmol) and Xantphos (0.0116 g, 0.02 mmol) in the presence of Cs2CO3 (0.0652 g, 0.2 mmol). The reaction was conducted in THF (5 mL) at 80° C. for 20 h. The title compound was isolated by flash column chromatography (silica gel, ethyl acetate:hexanes (v/v)=1:2) as purple mixture of two atropic isomers (0.032 g, 72%, α,α and αβ, =50%/50%). 1H NMR (300 MHz, CDCl3): δ 9.45 (d, J=4.8 Hz, 2H), 9.41 (d, J=4.8 Hz, 2H), 9.22 (m, 4H), 8.88 (d, J=4.8 Hz, 2H), 8.82 (m, 6H), 7.35 (m, 8H), 7.10 (m, 8H), 6.95 (m, 4H), 6.86 (m, 8H), 5.36 (m, 2H), 5.20 (m, 2H), 5.03 (m, 4H), 4.86 (m, 4H), 3.28 (m, 4H), 3.07 (dd, J=13.2, 3.6 Hz, 2H), 2.75 (dd, J=13.2, 3.3 Hz, 2H), 2.67 (s, 12H), 2.04 (s, 6H), 1.89 (s, 6H), 1.86 (s, 6H), 1.73 (s, 6H), −2.67 (s, 2H), −2.76 (s, 2H). 13C NMR (75 MHz, CDCl3): δ 159.5, 139.5, 139.3, 139.1, 138.2, 137.3, 137.2, 135.0, 128.8, 128.6, 128.5, 128.1, 127.9, 127.7, 127.1, 126.9, 119.9, 111.1, 110.8, 68.8, 66.3, 40.4, 21.9, 21.7, 21.6, 21.5. UV-vis (CHCl3, λmax, nm): 416, 512, 544, 590, 646. HRMS-MALDI ([M+H]+): calcd for C58H53N6O4, 897.4123, found 897.4109 with an isotope distribution pattern that is the same as calculated one.

Sources & evidence

ORD record
ord-6262e7745e1b46e190ae19577dafd8c9
Source dataset
uspto-grants-2008_08
Patent number
US07417142B2

Reaction notes

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