Water → HCID 11222940, compound

HRID 495104Notes

Reaction equation

HRID 495104 reaction equation
[C:1]([C:5]1[O:6][CH2:7][C@@H:8]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2I)[N:9]=1)([CH3:4])([CH3:3])[CH3:2].[Li]C(C)(C)C.[C:22]1([P:28]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)Cl)[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.O>CCOCC>[C:1]([C:5]1[O:6][CH2:7][C@@H:8]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[P:28]([C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[N:9]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 962WaterHCID 66180ChlorodiphenylphosphineHCID 12178025HCID 12178025, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 11222940HCID 11222940, compoundYield 40%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a solution of 4a (94 mg, 0.286 mmol) in 4 mL ether was added t-BuLi (1.7 M solution, 0.34 mL) at −78° C. The reaction mixture was stirred at −78° C. for 30 min before diphenylchlorophosphine (2.43 g, 11.0 mmol) was added slowly. The solution was allowed to warm to rt and was stirred overnight. Water was added. The aqueous layer was separated and extracted with CH2Cl2. The combined organic layers were dried with Na2SO4 and concentrated. The residue was purified by flash column chromatography to give 5a as a colorless oil (40%). [α]20D=−50.9 (c=2.0, CHCl3); 1H NMR (CD2Cl2, 360 MHz) δ 7.40-7.26 (m, 12H), 7.19 (dt, J=1.5 Hz, J=7.5 Hz, 1H), 6.93-6.89 (m, 1H), 5.82-5.75 (m, 1H), 4.24 (dd, J=is 8.4 Hz, J=10.2 Hz, 1H), 3.64 (dt, J=0.5 Hz, J=8.4 Hz, 1H), 1.28 (s, 9H); 13C NMR (CD2Cl2, 90 MHz) δ 175.8, 148.4 (d, J=24.0 Hz), 136.9 (d, J=10.2 Hz), 135.4-134.2 (m), 130.0-129.3 (m), 127.9 (br s), 126.8 (br s), 75.4 (d, J=4.4 Hz), 67.5 (m), 33.9, 28.3; 31P NMR (CD2Cl2, 145 MHz) δ-14.97; HRMS (M++1) m/z calculated for C25H27NOP 388.18248, found 388.17930.

Workup

  1. additionwas added slowly
  2. customThe aqueous layer was separated
  3. extractionextracted with CH2Cl2
  4. dry with materialThe combined organic layers were dried with Na2SO4
  5. concentrationconcentrated
  6. customThe residue was purified by flash column chromatography

Sources & evidence

ORD record
ord-0bc7a23f6bf147a2b74bd8d3c34228c8
Source dataset
uspto-grants-2009_05
Patent number
US07538228B2

Reaction notes

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