Triphenylphosphine → HCID 9931159, compound

HRID 1830937Notes

Reaction equation

HRID 1830937 reaction equation
C(OC([N:7]1[C:13]2[CH:14]=[C:15]([O:20][CH2:21][C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[C:16]([O:18][CH3:19])=[CH:17][C:12]=2[C:11](=[O:28])[N:10]2[CH:29]=[C:30]([CH2:32][C:33]([O:35][CH3:36])=[O:34])[CH2:31][C@H:9]2[C@@H:8]1O)=O)C=C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N1CCCC1>C(Cl)Cl.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>[CH3:19][O:18][C:16]1[CH:17]=[C:12]2[C:11]([N:10]3[C@H:9]([CH:8]=[N:7][C:13]2=[CH:14][C:15]=1[O:20][CH2:21][C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1)[CH2:31][C:30]([CH2:32][C:33]([O:35][CH3:36])=[O:34])=[CH:29]3)=[O:28]

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 31268PyrrolidineHCID 69622542HCID 69622542, compound

Product 1

HCID 9931159HCID 9931159, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

A catalytic amount of tetrakis(triphenylphosphine)palladium (5.0 mg, 4.33 μmol) was added to a stirred solution of the Alloc-protected carbinolamine 23 (88 mg, 0.17 mmol), triphenylphosphine (2.27 mg, 8.65 μmol) and pyrrolidine (13 mg, 0.18 mmol) in CH2Cl2 (15 mL). After 2 hours stirring at room temperature under a nitrogen atmosphere, TLC (80% EtOAc/Petroleum Ether) revealed the complete consumption of starting material. The solvent was evaporated in vacuo and the crude residue was purified by flash chromatography (60% EtOAc/Petroleum Ether) to afford the novel PBD (SJG-245) as a colourless glass (54 mg, 77%) which was repeatedly evaporated in vacuo with CHCl3 in order to provide the N10-C11 imine form 24: 1H NMR (270 MHz, CDCl3) (imine) δ7.80 (d, 1H, J=4.03 Hz, HC═N), 7.50 (s, 1Harom), 7.45-7.26 (m, 5Harom), 6.91 (br s, 1H, NCH═CCH2OC2CH3), 6.83 (s, 1Harom), 5.21-5.12 (m, 2H, PhCH2O), 3.94 (s, 3H, OCH3), 3.73 (s, 3H, CO2CH3), 3.23 (s, 2H, NCH═CCH2CO2CH3), 3.15 (m, 2H, NCH═CCH2CO2CH3CH2); 13C NMR (67.8 MHz, CDCl3) (imine) δ170.7 (CO2CH3), 162.7 (HC═N), 161.4 (NC═O), 150.9 (Carom), 148.1 (Carom), 140.1 (Carom), 136.0 (Carom), 128.7, 128.2 and 127.3 (BnC—Harom), 127.3 (NCH═CCH2CO2CH3), 119.2 (Carom), 117.5 (NCH═CCH2CO2CH3), 111.8 (C—Harom), 111.5 (C—Harom), 70.8 (PhCH2O), 56.2 (OCH3), 53.8 (NCHHC═N), 52.0 (CO2CH3), 37.4 (NCH═CCH2CO2CH3), 33.6 (NCH═CCH2CO2CH3CH2)

Workup

  1. customthe complete consumption of starting material
  2. customThe solvent was evaporated in vacuo
  3. customthe crude residue was purified by flash chromatography (60% EtOAc/Petroleum Ether)

Sources & evidence

ORD record
ord-fae219cfdfb14f3a8c1913ac3b9195ca
Source dataset
uspto-grants-2006_06
Patent number
US07067511B2

Reaction notes

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