Sodium borohydride → 6-Di-iso-propylphosphinomethyl-2,2'-bipyridine

HRID 2167168Notes

Reaction equation

HRID 2167168 reaction equation
[C:1]([P:5]([CH2:10][C:11]1[N:16]=[C:15]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=2)[CH:14]=[CH:13][CH:12]=1)[C:6](C)([CH3:8])[CH3:7])(C)([CH3:3])[CH3:2].[BH4-].[Na+]>CC(O)C>[CH:1]([P:5]([CH2:10][C:11]1[N:16]=[C:15]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=2)[CH:14]=[CH:13][CH:12]=1)[CH:6]([CH3:8])[CH3:7])([CH3:2])[CH3:3]

Participants

4

Reactant 2

HCID 4311764Sodium borohydrideHCID 532341466-((di-tert-Butylphosphino)methyl)-2,2'-bipyridine

Product 1

HCID 866998926-Di-iso-propylphosphinomethyl-2,2'-bipyridineYield 85%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

To a suspension of complex 5 (77 mg, 0.1 mmol) in 2-propanol (10 ml) was added a fine powder of NaBH4 (9.5 mg, 0.25 mmol). The mixture was stirred at room temperature for 12 hrs and then filtered. The resulting yellow solid was washed with 2-propanol (3×1.5 mL) and then dissolved in benzene (10 mL) and the solution was filtered. The yellow filtrate was evaporated to dryness under vacuum, yielding complex 6′ as a yellow solid which was dried under vacuum overnight to give 61 mg (85% yield). 31P{1H} NMR (C6D6): 61.6 (d, JPP=29.2 Hz), 67.9 (t, JPP=29.2 Hz). 1H NMR (C6D6): −14.0 (q, 1H, JPH=28.0 Hz, Ru—H), −0.84 (br s, 4H, BH4), 0.91 (q, 6H, JPH=JHH=8.0 Hz, P(CH(CH3)2)2), 0.87 (m, 12H, JPH=JHH=8.0 Hz, P(CH(CH3)2)2), 1.18 (q, JPH=JHH=8.0 Hz, 6H, P(CH(CH3)2)2), 1.44 (m, 2H, P(CH(CH3)2)2), 1.77 (m, 2H, P(CH(CH3)2)2), 2.85 (dt, 2H, JHH=16.0 Hz, JPH=4.0 Hz, −CHHP), 3.92 (dt, 2H, JHH=16.0 Hz, JPH=4.0 Hz, —CHHP), 6.56 (d, 2H, JHH=8.0 Hz, pyridine-H3, 5), 6.79 (t, 1H, JHH=8.0 Hz, pyridine-H4), 7.01 (d, 3H, JHH=8.0 Hz, P(C6H5)3), 7.12 (t, 6H, JHH=8.0 Hz, P(C6H5)3), 8.18 (t, 6H, JHH=8.0 Hz, P(C6H5)3). 13C{1H} NMR (C6D6): 18.0 (s, P(CH(CH3)2)2), 18.5 (s, P(CH(CH3)2)2), 19.6 (s, P(CH(CH3)2)2), 20.8 (s, P(CH(CH3)2)2), 25.6 (t, JPC=8.0 Hz, P(CH(CH3)2)2), 26.4 (t, JPC=11.6 Hz, CH2P), 39.2 (t, JPC=6.0 Hz, P(CH(CH3)2)2), 118.4 (t, JPC=2.5 Hz, Py-C3,5), 127.1 (d, JPC=9.0 Hz, m-C6H5—P), 128.8 (s, p-C6H5—P), 134.2 (s, Py-C4), 135.7 (d, JPC=10.1 Hz, o-C6H5—P), 142.0 (d, JPC=36.2 Hz, ipso-C6H5—P), 163.7 (t, JPC=4.5 Hz, py-C2,6).

Workup

  1. filtrationfiltered
  2. washThe resulting yellow solid was washed with 2-propanol (3×1.5 mL)
  3. dissolutiondissolved in benzene (10 mL)
  4. filtrationthe solution was filtered
  5. customThe yellow filtrate was evaporated to dryness under vacuum

Sources & evidence

ORD record
ord-f380b99a02dd46fc95a61f0c81d71e65
Source dataset
uspto-grants-2015_06
Patent number
US09045381B2

Reaction notes

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