Triphenylphosphine → HCID 11311008, compound

HRID 2116219Notes

Reaction equation

HRID 2116219 reaction equation
CC1C=CC(S(OCC2CC3C=CC=C(NC4C=CC=CC=4)C=3O2)(=O)=O)=CC=1.[N-]=[N+]=[N-].[Na+].[N:33]([CH2:36][CH:37]1[CH2:41][C:40]2[CH:42]=[CH:43][CH:44]=[C:45]([NH:46][C:47]3[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=3)[C:39]=2[O:38]1)=[N+]=[N-].[N-]=[N+]=[N-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>>[NH2:33][CH2:36][CH:37]1[CH2:41][C:40]2[CH:42]=[CH:43][CH:44]=[C:45]([NH:46][C:47]3[CH:48]=[CH:49][CH:50]=[CH:51][CH:52]=3)[C:39]=2[O:38]1

Participants

6

Reactant 5

HCID 11776TriphenylphosphineHCID 33557Sodium AzideHCID 33558AzideHCID 86599157HCID 86599157, compoundHCID 86599251HCID 86599251, compound

Product 1

HCID 11311008HCID 11311008, compoundYield 46%

Procedure

To a solution of (±)-(7-anilino-2,3-dihydro-1-benzofuran-2-yl)methyl 4-methylbenzenesulfonate (0.5 g, 1.5 mmol) in toluene (20 mL) was added bromobenzene (0.23 g, 1.5 mmol), dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (0.061 g, 0.075 mmol), 1,1′-bis(diphenylphosphino)ferrocene (0.125 g, 0.225 mmol), and sodium tert-butoxide (0.18 g, 1.875 mmol) and the reaction mixture was allowed to reflux 3 h. The solvent was removed in vacuo. The residue was washed with water (100 mL) and ethyl acetate (50 mL). The combined organic layers were washed with saturated aqueous sodium chloride, dried (magnesium sulfate), and the solvent removed in vacuo to provide a crude oil. Purification by flash column chromatography (silica, ethyl acetate:hexanes 3:10) afforded (±)-(7-anilino-2,3-dihydro-1-benzofuran-2-yl)methyl 4-methylbenzenesulfonate. Treatement of (±)-(7-anilino-2,3-dihydro-1-benzofuran-2-yl)methyl 4-methylbenzenesulfonate with sodium azide (0.18 g, 2.78 mmol) generally according to the procedure described for Intermediate 98 afforded (±)-2-(azidomethyl)-N-phenyl-2,3-dihydro-1-benzofuran-7-amine. Treatment of the azide with polymer-supported triphenylphosphine (1.09 g, 4.17 mmol) generally according to the procedure described for Example 21 provided 0.042 g, (46%) of (±)-2-(aminomethyl)-N-phenyl-2,3-dihydro-1-benzofuran-7-amine as a white solid, fumarate salt. mp 216-218° C.

Sources & evidence

ORD record
ord-119143f29bad439dba63a7157a8f8755
Source dataset
uspto-grants-2008_10
Patent number
US07435837B2

Reaction notes

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