Triphenylphosphine → HCID 69621480, compound

HRID 1826110Notes

Reaction equation

HRID 1826110 reaction equation
C(OC([N:7]1[C:13]2[CH:14]=[C:15]([O:20][CH3:21])[C:16]([O:18][CH3:19])=[CH:17][C:12]=2[C:11](=[O:22])[N:10]2[CH:23]=[C:24]([CH2:26][C:27]([O:29][CH3:30])=[O:28])[CH2:25][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)Cl.CO>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[C:15]([O:20][CH3:21])=[CH:14][C:13]2[N:7]=[CH:8][C@@H:9]3[CH2:25][CH:24]([CH2:26][C:27]([O:29][CH3:30])=[O:28])[CH2:23][N:10]3[C:11](=[O:22])[C:12]=2[CH:17]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 31268PyrrolidineHCID 21584188Chloroform methanolHCID 69621501HCID 69621501, compound

Product 1

HCID 69621480HCID 69621480, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

A catalytic amount of tetrakis(triphenylphosphine)palladium (44.0 mg, 38.0 μmol) was added to a stirred solution of the Alloc-protected carbinolamine 41 (0.66 g, 1.53 mmol), triphenylphosphine (20.0 mg, 77.0 mmol) and pyrrolidine (114 mg, 1.60 mmol) in CH2Cl2, (100 mL). After 2 hours stirring at room temperature under a nitrogen atmosphere, TLC (99% CHCl3/MeOH) revealed the complete consumption of starting material. The solvent was evaporated in vacuo and the crude residue was purified by flash chromatography (98% CHCl3/MeOH) to afford the PBD (42, AN-SJG, UP2065) as an orange glass which was repeatedly evaporated in vacuo with CHCl3 in order to provide the N10-C11 imine form (481 mg, 95%): [α]22D+401.84° (c=1.00, CHCl3); 1H NMR (270 MHz, CDCl3) δ 7.87-7.85 (m, 1H), 7.49 (s, 1H), 6.93 (s, 1H), 6.81 (s, 1H), 4.34-4.27 (m, 1H), 3.95 (s, 3H), 3.93 (s, 3H), 3.74 (s, 3H), 3.34 (d, 1H, J=16.85 Hz), 3.24 (s, 2H), 3.19-3.10 (m, 1H); 13C NMR (67.8 MHz, CDCl3) δ 170.6, 162.7, 161.4, 151.8, 147.7, 140.4, 126.5, 119.0, 117.4, 111.5, 109.8, 56.2, 56.1, 53.8, 52.1, 37.4, 33.6; MS (EI), m/z (relative intensity) 332 (M+.+2, 5), 331 (M+.+1, 9), 330 (M+., 41), 329 (28), 328 (100), 313 (18), 272 (8), 271 (24), 270 (14), 269 (27), 262 (7), 257 (12), 255 (5), 242 (6), 225 (7), 197 (4), 192 (16), 191 (16), 183 (6), 164 (14), 136 (11), 135 (9), 106 (9), 80 (17), 53 (5); IR (CHCl3) 3329 (br), 3112, 2952, 2842, 1737, 1626, 1602, 1512, 1453, 1436, 1381, 1356, 1246, 1213, 1173, 1096, 1069, 1008, 875, 840, 786, 666, 620, 574, 537 cm−1; exact mass calcd for C17H18N2O5 m/e 330.1216, obsd m/e 330.1237.

Workup

  1. customthe complete consumption of starting material
  2. customThe solvent was evaporated in vacuo
  3. customthe crude residue was purified by flash chromatography (98% CHCl3/MeOH)
  4. customto afford the PBD (42, AN-SJG, UP2065) as an orange glass which
  5. customwas repeatedly evaporated in vacuo with CHCl3 in order

Sources & evidence

ORD record
ord-6020a5c337384c949eb63ff7b09c9e08
Source dataset
uspto-grants-2006_05
Patent number
US07049311B1

Reaction notes

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