Triphenylphosphine → HCID 86613988, compound

HRID 490056Notes

Reaction equation

HRID 490056 reaction equation
[CH2:1]([O:33][CH:34]1[C@H:38]2[C@H:39](O)[N:40](C(OCC=C)=O)[C:41]3[CH:48]=[CH:47][C:46]([O:49][CH3:50])=[CH:45][C:42]=3[C:43](=[O:44])[N:37]2[CH2:36]/[C:35]/1=[CH:58]/[CH3:59])[CH2:2][CH2:3][CH2:4][CH2:5][O:6][CH:7]1[C@H:11]2[C@H:12](O)[N:13](C(OCC=C)=O)[C:14]3[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][C:15]=3[C:16](=[O:17])[N:10]2[CH2:9]/[C:8]/1=[CH:31]/[CH3:32].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>[CH2:1]([O:33][CH:34]1[C@@H:38]2[CH:39]=[N:40][C:41]3[CH:48]=[CH:47][C:46]([O:49][CH3:50])=[CH:45][C:42]=3[C:43](=[O:44])[N:37]2[CH2:36]/[C:35]/1=[CH:58]/[CH3:59])[CH2:2][CH2:3][CH2:4][CH2:5][O:6][CH:7]1[C@@H:11]2[CH:12]=[N:13][C:14]3[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][C:15]=3[C:16](=[O:17])[N:10]2[CH2:9]/[C:8]/1=[CH:31]/[CH3:32]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 31268PyrrolidineHCID 21584188Chloroform methanolHCID 86613989HCID 86613989, compound

Product 1

HCID 86613988HCID 86613988, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

A catalytic amount of tetrakis(triphenylphosphine)palladium (14.4 mg, 12.5 μmol) was added to a stirred solution of the bis-alloc-carbinolamine 5 (200 mg, 0.25 mmol), triphenylphosphine (6.30 mg, 24.1 μmol) and pyrrolidine (33 mg, 40.1 μL 0.48 mmol) in CH2Cl2 (13 mL) under a nitrogen atmosphere. The reaction mixture was allowed to warm to room temperature and the progress of reaction monitored by TLC (95:5 v/v CHCl3/MeOH). After two and a half hours TLC revealed the reaction was complete to give a spot which fluoresced brightly under UV light. The solvent was evaporated under reduced pressure and the resulting residue subjected to flash chromatography (98:2 v/v CHCl3/MeOH) to give the bis-imine target molecule 1 as a pale orange glass which was repeatedly evaporated in vacuo with CHCl3 to provide the imine form. Yield=160 mg (Quant); [α]21D=+937° (c=0.641, CHCl3); 1H NMR (250 MHz, CDCl3) δ 7.67 (d, 2H, J=4.5 Hz), 7.50 (s, 2H) 6.80 (s, 2H), 5.63-5.55 (m, 2H), 4.38-3.96 (m, 8H), 3.94 (s, 6H), 3.86-3.80 (m, 2H), 3.20-3.03 (m, 2H), 2.90 (d, 2H, J=15.8 Hz), 2.00-1.91 (m, 4H), 1.76-1.68 (m, 8H); 13C NMR (62.9 MHz, CDCl3) δ 164.9, 163.0, 150.8, 147.8, 140.6, 132.9, 119.8, 119.3, 111.4, 110.3, 68.7, 56.1, 53.4, 48.3, 35.3, 28.6, 22.5, 14.9; MS (FAB) m/z (relative intensity) 613 ([M+H]+, 52), 443 (26), 421 (22), 329 (100), 307 (71), 242 (35), 220 (38); IR (CHCl3) 3220 (br), 2940, 2859, 1697, 1602, 1560, 1508, 1458, 1432, 1382, 1341, 1263, 1217, 1132, 1098, 1065, 1007, 875, 666 cm−1; HRMS [M+H]+ calcd for C35H41N4O6 m/z 613.3026, found (FAB) m/z 613.3047.

Workup

  1. customthe progress of reaction
  2. waitAfter two and a half hours TLC revealed
  3. customto give a spot which
  4. customThe solvent was evaporated under reduced pressure

Sources & evidence

ORD record
ord-ad18f6316f3e47adad6f25d1b01bc469
Source dataset
uspto-grants-2009_05
Patent number
US07528126B2

Reaction notes

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