Triphenylphosphine → HCID 69621480, compound

HRID 1830939Notes

Reaction equation

HRID 1830939 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 μmol) 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) δ7.87-7.85 (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) δ170.6, 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 (+. +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 C17H18N2O, 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-a99ef9c48c7f4a1180550e96cf4b7378
Source dataset
uspto-grants-2006_06
Patent number
US07067511B2

Reaction notes

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