1,2-Bis(diphenylphosphino)ethane → HCID 66832700, compound

HRID 579604Notes

Reaction equation

HRID 579604 reaction equation
C1(P(C2C=CC=CC=2)CCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:29][C:30]1([CH3:37])[C:34]([CH3:36])([CH3:35])[O:33][BH:32][O:31]1.[C:38]([NH:41][C:42]([CH:54]1[CH2:59][CH2:58][N:57]([C:60]([O:62][CH2:63][C:64]2[CH:69]=[CH:68][CH:67]=[CH:66][CH:65]=2)=[O:61])[CH2:56][CH2:55]1)([CH2:50][CH2:51][CH:52]=[CH2:53])[C:43]([NH:45][C:46]([CH3:49])([CH3:48])[CH3:47])=[O:44])(=[O:40])[CH3:39]>C1COCC1.[Ir+].ClC1CCC=CCCC=1>[C:38]([NH:41][C:42]([CH:54]1[CH2:55][CH2:56][N:57]([C:60]([O:62][CH2:63][C:64]2[CH:69]=[CH:68][CH:67]=[CH:66][CH:65]=2)=[O:61])[CH2:58][CH2:59]1)([CH2:50][CH2:51][CH2:52][CH2:53][B:32]1[O:33][C:34]([CH3:36])([CH3:35])[C:30]([CH3:37])([CH3:29])[O:31]1)[C:43]([NH:45][C:46]([CH3:49])([CH3:47])[CH3:48])=[O:44])(=[O:40])[CH3:39]

Participants

6

Reactant 3

HCID 742671,2-Bis(diphenylphosphino)ethaneHCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolaneHCID 66833672HCID 66833672, compound

Product 1

HCID 66832700HCID 66832700, compoundYield 71%

Reagents, catalysts & solvents 2

HCID 178478077HCID 178478077, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

While under an argon atmosphere, a solution of 1,2-bis(diphenylphosphino)ethane (306 mg, 0.77 mmol) and chloro-1,5-cyclooctadiene iridium (I) dimer (258 mg, 0.39 mmol) in anhydrous THF (30 mL) was treated with 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.48 g, 1.67 mL, 11.6 mmol) in one portion. After stirring for 15 minutes the solution was cooled to 5° C. (ice-water batch) and treated with benzyl 4-(2-acetamido-1-(tert-butylamino)-1-oxohex-5-en-2-yl)piperidine-1-carboxylate (3.42 g, 7.70 mmol) in one portion. After the addition was complete, the cooling bath was removed and the reaction mixture was allowed to warm up to room temperature. After 2 hours of stirring the reaction was quenched with saturated aqueous sodium bicarbonate (50 mL) and extracted using ethyl acetate (2×150 mL). The organic layer was dried over MgSO4, filtered and concentrated. MPLC purification (100 g column, 40-80% ethyl acetate in heptane) gave benzyl 4-(2-acetamido-1-(tert-butylamino)-1-oxo-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexan-2-yl)piperidine-1-carboxylate as a colorless oil (3.10 g, 71% yield). 1H NMR (CDCl3, 300 MHz) δ 7.36-7.30 (m, 5H), 6.94 (bs, 1H), 5.46 (s, 1H), 5.10 (s, 2H), 4.36-4.10 (m, 2H), 2.86-2.60 (m, 3H), 2.40-2.28 (bt, J=12.3 Hz, 1H), 1.98 (s, 3H), 1.78-1.61 (m, 2H), 1.49-1.17 (m, 5H), 1.33 (s, 9H), 1.20 (s, 8H), 1.12-0.94 (m, 2H), 0.73 (t, J=7.8 Hz, 2H).

Workup

  1. additionAfter the addition
  2. customthe cooling bath was removed
  3. stirringAfter 2 hours of stirring the reaction
  4. customwas quenched with saturated aqueous sodium bicarbonate (50 mL)
  5. extractionextracted
  6. dry with materialThe organic layer was dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customMPLC purification (100 g column, 40-80% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-30d5ad27943341a095dbcf5cd7ee9440
Source dataset
uspto-grants-2015_05
Patent number
US09040703B2

Reaction notes

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