Hydrochloric Acid → t-butyl 3-hydroxy-(R)-5-[(tetrahydro-2H-pyran-2-yl) oxy]-2-[(S)-p-tolylsulfinyl]-hexadecanoate

HRID 1681969Notes

Reaction equation

HRID 1681969 reaction equation
[C:1]1([CH3:17])[CH:6]=[CH:5][C:4]([S@:7]([CH2:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])=[O:8])=[CH:3][CH:2]=1.C([Mg]Br)(C)(C)C.[O:24]1[CH2:29][CH2:28][CH2:27][CH2:26][CH:25]1[O:30][C@H:31]([CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH3:45])[CH2:32][CH:33]=[O:34].Cl>CCOCC.C1COCC1>[OH:34][CH:33]([CH2:32][CH:31]([O:30][CH:25]1[CH2:26][CH2:27][CH2:28][CH2:29][O:24]1)[CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH3:45])[C@@H:9]([S@@:7]([C:4]1[CH:3]=[CH:2][C:1]([CH3:17])=[CH:6][CH:5]=1)=[O:8])[C:10]([O:12][C:13]([CH3:14])([CH3:16])[CH3:15])=[O:11]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 11118618t-butyl [(S)-p-tolylsulfinyl]acetateHCID 14852578HCID 14852578, compoundHCID 178418586HCID 178418586, compound

Product 1

HCID 67855726t-butyl 3-hydroxy-(R)-5-[(tetrahydro-2H-pyran-2-yl) oxy]-2-[(S)-p-tolylsulfinyl]-hexadecanoateYield 67%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

G)a) 16.5 g of t-butyl [(S)-p-tolylsulfinyl]acetate were dissolved in a mixture of 600 ml of ether and 60 ml of THF and cooled to -78° C. 43 ml of t-butylmagnesium bromide were then added dropwise in such a manner that the temperature remained below -70° C. After stirring at -78° C. for 1 hour 13.4 g of (R)-3-[(tetrahydro-2H-pyran-2yl)oxy]-tetradecanal in 100 ml of THF were added dropwise. After 2 hours at -78° C. the reaction mixture was hydrolyzed with 2N hydrochloric acid and the solvent was evaporated off. The reaction mixture remaining behind was extracted with ether and the ethereal phase was dried and evaporated. After chromatography on silica gel there were obtained 14.9 g of t-butyl 3-hydroxy-(R)-5-[(tetrahydro-2H-pyran-2-yl) oxy]-2-[(S)-p-tolylsulfinyl]-hexadecanoate (67% yield). m.p. 97°-98° C.

Workup

  1. customremained below -70° C
  2. additionwere added dropwise
  3. customthe solvent was evaporated off
  4. extractionThe reaction mixture remaining behind was extracted with ether
  5. customthe ethereal phase was dried
  6. customevaporated

Sources & evidence

ORD record
ord-bead6e1ba1334e5fadfa8248f9288ce0
Source dataset
uspto-grants-1992_12
Patent number
US05175186

Reaction notes

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