Tributylvinyltin → HCID 178435350, compound

HRID 2225035Notes

Reaction equation

HRID 2225035 reaction equation
[C:1]12[CH:24]=[C:22]3[N:23]=[C:19]([CH:20]=[CH:21]3)[CH:18]=[C:16]3[NH:17][C:13]([CH:14]=[CH:15]3)=[CH:12][C:10]3=[N:11][C:7]([CH:8]=[CH:9]3)=[CH:6][C:4]([NH:5]1)=[CH:3][CH:2]=2.[CH:25]([Sn](CCCC)(CCCC)CCCC)=[CH2:26]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:25]([C:3]1[CH:2]=[C:1]2[CH:24]=[C:22]3[N:23]=[C:19]([CH:18]=[C:16]4[NH:17][C:13](=[CH:12][C:10]5[CH:9]=[CH:8][C:7](=[CH:6][C:4]=1[NH:5]2)[N:11]=5)[CH:14]=[CH:15]4)[CH:20]=[CH:21]3)=[CH2:26]

Participants

4

Reactant 2

HCID 81998TributylvinyltinHCID 13770524121H,22H-Porphine

Product 1

HCID 178435350HCID 178435350, compoundYield 77%

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Procedure

One porphyrin that was not available via this route was the vinyl-porphyrin Zn10, owing to the lack of access to 5-vinyldipyrromethane (vide supra). The synthesis of Zn10 was achieved following the route outlined in Scheme 6. Diacyldipyrromethane 3248 was reduced with NaBH4 and the resulting 32-diol was condensed with dipyrromethane (36)41,49 in CH2Cl2 containing Yb(OTf)3 at room temperature. Subsequent oxidation with DDQ afforded free base porphyrin 37 in 33% yield. Porphyrin 37 was iodinated at the meso-position using I2 and (CF3CO2)2IC6H5 in CHCl3/pyridine50 to furnish free base porphyrin 8 in 82% yield. Zinc insertion afforded Zn8 in 75% yield. Porphyrin Zn8 was then subjected to a Stille cross-coupling reaction51 with (vinyl)tributyltin and Pd(PPh3)4 to afford vinylporphyrin Zn10 in 77% yield.

Sources & evidence

ORD record
ord-0b71ce1e340541dc869a29b148d0069b
Source dataset
uspto-grants-2008_05
Patent number
US07378520B2

Reaction notes

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