Cesium carbonate → 21H,22H-Porphine

HRID 2220779Notes

Reaction equation

HRID 2220779 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.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: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

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 178440595HCID 178440595, 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(3′,5′-di-tert-butylphenyl)porphyrin (0.043 g, 0.05 mmol) with (R)-(+)-4-benzyl-2-oxazolidinone (0.0708 g, 0.4 mmol), using Pd2(dba)3 (0.0023 g, 0.0025 mmol) and Xantphos (0.0058 g, 0.01 mmol) in the presence of Cs2CO3 (0.0652 g, 0.2 mmol). The reaction was conducted in THF (5 mL) at 80° C. for 22 h. The title compound was isolated by flash column chromatography (silica gel, ethyl acetate:hexanes (v/v)=1:3) as purple mixture of two atropic isomers (0.039 g, 79%, α,α/α,β=50%/50%). 1H NMR (300 MHz, CDCl3): δ 9.48 (d, J=4.8 Hz, 2H), 9.46 (d, J=4.8 Hz, 2H), 9.27 (d, J=4.8 Hz, 2H), 9.25 (d, J=4.8 Hz, 2H), 9.08 (d, J=4.8 Hz, 2H), 9.04 (d, J=4.8 Hz, 2H), 9.02 (d, J=4.8 Hz, 2H), 9.00 (d, J=4.8 Hz, 2H), 8.24 (s, 2H), 8.12 (d, J=0.9 Hz, 2H), 8.07 (d, J=0.9 Hz, 2H), 7.93 (s, 2H), 7.86 (s, 4H), 7.08 (m, 12H), 6.88 (m, 8H), 5.40 (m, 2H), 5.27 (m, 2H), 5.03 (q, J=9.0 Hz, 4H), 4.84 (q, J=7.8 Hz, 4H), 3.27 (m, 4H), 3.00 (m, 2H), 2.77 (m, 2H), 1.61 (s, 18H), 1.59 (s, 18H), 1.56 (s, 18H), 1.53 (s, 18H), −2.76 (s, 2H), −2.81 (s, 2H). 13C NMR (75 MHz, CDCl3): δ 159.5, 159.4, 149.3, 149.1, 149.0, 140.2, 140.0, 135.1, 130.1, 130.1, 129.8, 129.8, 128.8, 128.7, 127.1, 127.0, 122.9, 121.5, 111.4, 111.2, 68.9, 68.8, 66.3, 40.5, 40.4, 35.1, 31.8, 31.7. UV-vis (CHCl3, λmax, nm): 419, 514, 549, 591, 646. HRMS-MALDI ([M+H]+): calcd for C68H73N6O4, 1037.5688; found: 1037.5677 with an isotope distribution pattern that is the same as calculated one.

Sources & evidence

ORD record
ord-9f409c097efc42d4b8225620bae1e65c
Source dataset
uspto-grants-2008_08
Patent number
US07417142B2

Reaction notes

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