Diethylamine → 2,3-Bis(2R,5R)(2,5-dimethylphospholan-1-yl)-1-benzothiophene

HRID 2217122Notes

Reaction equation

HRID 2217122 reaction equation
[PH2:1][C:2]1[S:6][C:5]2[CH:7]=[CH:8][CH:9]=[CH:10][C:4]=2[C:3]=1[PH2:11].[Li]N(CC)CC.N(CC)CC.[Li]CCCC.C[CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34].[CH3:35][C@H:36](O)[CH2:37][CH2:38][C@@H:39](O)[CH3:40]>C1COCC1.C(OCC)C.O>[CH3:40][C@@H:39]1[CH2:38][CH2:37][C@@H:36]([CH3:35])[P:1]1[C:2]1[S:6][C:5]2[CH:7]=[CH:8][CH:9]=[CH:10][C:4]=2[C:3]=1[P:11]1[C@H:33]([CH3:34])[CH2:32][CH2:31][C@H:30]1[CH3:29]

Participants

9

Reactant 5

HCID 8021DiethylamineHCID 69502882,5-Hexanediol, (2S,5S)-HCID 116584572,3-Bisphosphinobenzo[b]thiopheneHCID 178418713HCID 178418713, compound3×HCID 178418722HCID 178418722, compound

Product 1

HCID 162169732,3-Bis(2R,5R)(2,5-dimethylphospholan-1-yl)-1-benzothiopheneYield 53%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent5×

Procedure

Under argon, a degassed solution of 1.98 g (10 mmol) 2.3-bisphosphinobenzo[b]thiophene in 30 ml THF is treated with 5.5 ml (11 mmol) of a 2N solution of LiNEt2 (freshly prepared from Et2NH and 2.7 M n-BuLi/heptane) in THF. The resulting red solution is added to a degassed solution of the cyclic sulfate derived from (2S,5S)-2,5-hexanediol (3.6 g, 20 mmol) in 40 ml THF at 0° C. The mixture is stirred for 2 h during which time decolorization can be observed. Further 5.5 ml (11 mmol) of a 2N solution of LiNEt2 in THF is added and stirring is continued for 2 h. Then 11 ml (22 mmol) of a 2N solution of LiNEt2 in THF is added. At the end of the addition the mixture becomes more viscous and a precipitate can be observed. After stirring for another 2 h at room temperature 100 ml water and 100 ml diethyl ether are added. The organic layer is removed via double ended needle and the extraction is repeated with 50 ml of diethyl ether. The ether layer is removed as described before, the combined organic layers are dried over sodium sulfate and evaporated yielding 1.91 g (53%) of the title compound as a pale yellow oil.

Workup

  1. stirringstirring
  2. waitis continued for 2 h
  3. additionAt the end of the addition the mixture
  4. additionare added
  5. customThe organic layer is removed
  6. extractionthe extraction
  7. customThe ether layer is removed
  8. dry with materialare dried over sodium sulfate
  9. customevaporated

Sources & evidence

ORD record
ord-13a47a9aedab46b8b0e9bf9ccde9bfc4
Source dataset
uspto-grants-2008_08
Patent number
US07407910B2

Reaction notes

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