Hydrochloric Acid → HCID 90388282, compound

HRID 2201730Notes

Reaction equation

HRID 2201730 reaction equation
[CH3:1][C@@:2]12[C:18](=[O:19])[CH2:17][CH2:16][C@H:15]1[CH2:14][C@@H:13]1[C@H:4]([CH2:5][CH2:6][C@@H:7]3[C@H:12]1[CH2:11][CH2:10][C:9](=[O:20])[CH2:8]3)[CH2:3]2.C(O[AlH-](OC(C)(C)C)OC(C)(C)C)(C)(C)C.[Li+].Cl>C1COCC1>[OH:20][C@@H:9]1[CH2:8][C@H:7]2[C@H:12]([C@H:13]3[C@H:4]([CH2:5][CH2:6]2)[CH2:3][C@:2]2([CH3:1])[C:18](=[O:19])[CH2:17][CH2:16][C@H:15]2[CH2:14]3)[CH2:11][CH2:10]1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 16684435Lithium tritertbutoxyaluminohydrideHCID 90388260HCID 90388260, compound

Product 1

HCID 90388282HCID 90388282, compoundYield 56%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of compound 13 (145 mg containing the unseparated 4aR diastereomer, 0.54 mmol) in THF (10 mL) was slowly added lithium tri-t-butyloxyaluminohydride at −40° C. After 2 h, 6 N HCl was added at −40° C. and the reaction was warmed to room temperature for 30 min. The product was extracted into EtOAc (50 mL×2). The combined extracts were dried, filtered, and removed. The residue was purified by flash column chromatography (silica gel eluted with 25% EtOAc in hexanes) and the product from the 4aR diastereomer separated to afford pure compound 14 (82 mg, 56%): mp 175-177° C.; [α]D20 +34.5 (c 0.22, CHCl3); 1H NMR (CDCl3) δ 3.58-3.49 (m, 1H), 0.76 (s, 3H); 13C NMR (CDCl3) δ 221.1, 71.4, 47.9, 45.7, 40.1, 39.2, 38.8, 38.5, 36.2, 35.6, 35.5, 31.7, 29.6, 29.3, 28.4, 25.5, 24.1, 13.5; IR νmax 3398, 1736 cm−1. Anal. Calcd for (C18H28O2): C, 78.21; H, 10.21. Found: C, 78.12; H, 10.40.

Workup

  1. customat −40° C
  2. extractionThe product was extracted into EtOAc (50 mL×2)
  3. customThe combined extracts were dried
  4. filtrationfiltered
  5. customremoved
  6. customThe residue was purified by flash column chromatography (silica gel eluted with 25% EtOAc in hexanes)
  7. customthe product from the 4aR diastereomer separated

Sources & evidence

ORD record
ord-9932426e9a734bb5a181edc7bfa64824
Source dataset
uspto-grants-2016_06
Patent number
US09365502B2

Reaction notes

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