Triphenylphosphine → HCID 9838363, compound

HRID 1830954Notes

Reaction equation

HRID 1830954 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[CH2:23][C:24](=[CH2:26])[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][C:24](=[CH2:26])[CH2:23][N:10]3[C:11](=[O:22])[C:12]=2[CH:17]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 31268PyrrolidineHCID 21584188Chloroform methanolHCID 69460387HCID 69460387, compound

Product 1

HCID 9838363HCID 9838363, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

A catalytic amount of tetrakis(triphenylphosphine)palladium (32.4 mg, 28.1 μmol) was added to a stirred solution of the Alloc-protected carbinolamine 73 (0.42 g, 1.12 mmol), triphenylphosphine (14.7 mg, 56.2 μmol) and pyrrolidine (83.9 mg, 1.18 mmol) in CH2Cl2 (55 mL). After 2.5 hours stirring at room temperature under a nitrogen atmosphere, TLC (95% CHCl3/MeOH) revealed the complete consumption of starting material. The solvent was evaporated in vacuo and the crude residue was purified by flash chromatography (CHCl3) to afford the novel PBD (74, MMY-SJG, UP2064) as a yellow oil which was repeatedly evaporated in vacuo with CHCl3 in order to provide the N10-C11 imine form (259 mg, 85%): [α]22D=+583.14° (c=1.42, CHCl3); 1H NMR (270 MHz, CDCl3) δ7.69 (d, 1H, J=4.39 Hz), 7.51 (s, 1H), 6.82 (s, 1H), 5.21-5.17 (m, 2H), 4.44-4.23 (m, 2H), 3.96-3.81 (m, 7H), 3.17-3.08 (m, 1H), 2.95 (d, 1H, J=14.29 Hz); 13C NMR (67.8 MHz, CDCl3) δ164.7, 162.6, 151.5, 147.6, 141.6, 140.8, 119.8, 111.2, 109.4, 109.4, 56.2, 56.1, 53.8, 51.4, 35.5; MS (EI), m/z (relative intensity) 273 (M+. +1, 16), 272 (M+., 100), 271 (35), 270 (9), 255 (5), 243 (7), 241 (7), 230 (6), 228 (6), 226 (5), 212 (3), 192 (4), 191 (16), 165 (4), 164 (19), 163 (4), 136 (22), 93 (6), 82 (7), 80 (3), 53 (3); IR (NEAT) 3312 (br), 3083, 2936, 2843, 1624, 1603, 1505, 1434, 1380, 1264, 1217, 1180, 1130, 1096, 1069, 1007, 935, 895, 837, 786, 696, 666, 594, 542 cm−1; exact mass calcd for C11H16N2O3 m/e 272.1161, obsd m/e 272.1154.

Workup

  1. customthe complete consumption of starting material
  2. customThe solvent was evaporated in vacuo
  3. customthe crude residue was purified by flash chromatography (CHCl3)
  4. customto afford the novel PBD (74, MMY-SJG, UP2064) as a yellow oil which
  5. customwas repeatedly evaporated in vacuo with CHCl3 in order

Sources & evidence

ORD record
ord-8b5dcabf15754e2c9fdbb5bf606746ea
Source dataset
uspto-grants-2006_06
Patent number
US07067511B2

Reaction notes

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