Diethylamine → Chloro[(S)-(-)-2,2 inverted exclamation mark-bis[di(3,5-xylyl)phosphino]-1,1 inverted exclamation mark-binaphthyl][(2S)-(+)-1-(4-methoxyphenyl)-1-(4-methoxyphenyl-kC)-3-methyl-1,2-butanediamine]ruthenium(II)

HRID 1773165Notes

Reaction equation

HRID 1773165 reaction equation
CC1C=CC(C(C)C)=CC=1.[CH3:11][C:12]1[CH:17]=[C:16]([P:18]([C:56]2[CH:61]=[C:60]([CH3:62])[CH:59]=[C:58]([CH3:63])[CH:57]=2)[C:19]2[CH:28]=[CH:27][C:26]3[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=3)[C:20]=2[C:29]2[C:38]3[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=3)[CH:32]=[CH:31][C:30]=2[P:39]([C:48]2[CH:53]=[C:52]([CH3:54])[CH:51]=[C:50]([CH3:55])[CH:49]=2)[C:40]2[CH:45]=[C:44]([CH3:46])[CH:43]=[C:42]([CH3:47])[CH:41]=2)[CH:15]=[C:14]([CH3:64])[CH:13]=1.[Cl:65][Ru:66]Cl.C(NCC)C.[CH3:73][CH:74]([C@H:76]([NH2:95])[C:77]([NH2:94])([C:86]1[CH:91]=[CH:90][C:89]([O:92][CH3:93])=[CH:88][CH:87]=1)[C:78]1[CH:83]=[CH:82][C:81]([O:84][CH3:85])=[CH:80][CH:79]=1)[CH3:75]>CO>[CH3:63][C:58]1[CH:57]=[C:56]([P:18]([C:16]2[CH:15]=[C:14]([CH3:64])[CH:13]=[C:12]([CH3:11])[CH:17]=2)[C:19]2[CH:28]=[CH:27][C:26]3[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=3)[C:20]=2[C:29]2[C:38]3[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=3)[CH:32]=[CH:31][C:30]=2[P:39]([C:48]2[CH:49]=[C:50]([CH3:55])[CH:51]=[C:52]([CH3:54])[CH:53]=2)[C:40]2[CH:45]=[C:44]([CH3:46])[CH:43]=[C:42]([CH3:47])[CH:41]=2)[CH:61]=[C:60]([CH3:62])[CH:59]=1.[CH3:75][CH:74]([C@H:76]([NH2:95])[C:77]([NH2:94])([C:78]1[CH:79]=[CH:80][C:81]([O:84][CH3:85])=[CH:82][CH:83]=1)[C:86]1[CH:87]=[CH:88][C:89]([O:92][CH3:93])=[CH:90][CH:91]=1)[CH3:73].[Cl-:65].[Ru+:66]

Participants

5

Reactant 3

HCID 8021DiethylamineHCID 10964285(2S)-1,1-Bis(4-methoxyphenyl)-3-methylbutane-1,2-diamineHCID 72376324chloro[(S)-2,2'-bis(bis(3,5-dimethylphenyl)phosphino)-1,1'-binaphthyl](p-cymene)ruthenium(II) chloride

Product 1

HCID 91972051Chloro[(S)-(-)-2,2 inverted exclamation mark-bis[di(3,5-xylyl)phosphino]-1,1 inverted exclamation mark-binaphthyl][(2S)-(+)-1-(4-methoxyphenyl)-1-(4-methoxyphenyl-kC)-3-methyl-1,2-butanediamine]ruthenium(II)Yield 98%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
50 °C

Procedure

Under a nitrogen gas, [RuCl2(p-cymene)]2 3.07 g (5.0 mmol), (S)-XylBINAP 7.35 g (10.0 mmol) and methanol 110 mL were added to a 200 mL 4-neck flask. The mixture was heated to 50° C. and stirred for 2 hours to prepare [RuCl(p-cymene)((S)-xylbinap)]Cl. The reaction solution was cooling down to room temperature, then diethylamine 736 mg (10 mmol) and (S)-DAIPEN 3.48 g (11.1 mmol) were added to the reaction solution, and stirred for 3 hours at 60° C. After concentration, the residue was dissolved in butyl acetate and the precipitated salts were separated by filtration. The filtrate was concentrated and the mixture added with heptane (110 mL) was cooling down to −10° C. The precipitated crystals were filtered to obtain the title compound (11.62 g) with yield of 98%.

Workup

  1. temperatureThe reaction solution was cooling down to room temperature
  2. stirringstirred for 3 hours at 60° C
  3. concentrationAfter concentration
  4. dissolutionthe residue was dissolved in butyl acetate
  5. customthe precipitated salts were separated by filtration
  6. concentrationThe filtrate was concentrated
  7. additionthe mixture added with heptane (110 mL)
  8. temperaturewas cooling down to −10° C
  9. filtrationThe precipitated crystals were filtered

Sources & evidence

ORD record
ord-d0c7ecaaa869412f8ffd1554d5c7e171
Source dataset
uspto-grants-2016_02
Patent number
US09255049B2

Reaction notes

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