Pyridine → HCID 12066280, compound

HRID 1264184Notes

Reaction equation

HRID 1264184 reaction equation
[C:1]([O:4][C@@H:5]([CH2:8][CH2:9][C@H:10]([OH:13])[CH2:11][OH:12])[C:6]#[CH:7])(=[O:3])[CH3:2].N1C=CC=CC=1.[C:20]1([CH3:30])[CH:25]=[CH:24][C:23]([S:26](Cl)(=[O:28])=[O:27])=[CH:22][CH:21]=1>C(Cl)Cl>[C:1]([O:4][C@@H:5]([CH2:8][CH2:9][C@H:10]([OH:13])[CH2:11][O:12][S:26]([C:23]1[CH:24]=[CH:25][C:20]([CH3:30])=[CH:21][CH:22]=1)(=[O:28])=[O:27])[C:6]#[CH:7])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 1049PyridineHCID 73974-Toluenesulfonyl chlorideHCID 12066279HCID 12066279, compound

Product 1

HCID 12066280HCID 12066280, compoundYield 10%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of(3S,6S)-3-acetoxy-6,7-dihydroxy-hept-1-yne 14 (4.3 g, 23.1 mmol) in CH2Cl2 (50 mL) containing pyridine (3.7 mL, 46.2 mmol) was cooled to 0° C. and treated with p-toluene sulfonyl chloride (4.4 g, 23.1 mmol) and stirred at room temperature for 5 h. The reaction mixture was diluted with CH2Cl2 (25 mL) and washed with aqueous CuSO4 solution (2×25 mL) followed by water (2×25 n mL). Organic layer was dried (Na2SO4), evaporated and purified by chromatography (Si-gel, 15% EtOAc-hexane); first eluted was (3S,6S)-3-acetoxy-6,7-di-p-toluene sulfonyloxy-hept-1-yne 15a (1.14 g) in 10% yield as a yellow syrup. 1HNMR (CDCl3, 200 MHz): δ1.48-1.8 (m, 4H, H-3,4), 2.0 (s, 3H, OAc), 2.31 (d, 1H, J 2.5 Hz, H-7) 2.4 (s, 3H, Ar—CH3), 3.94 (d, 2H, J 4.5 Hz, H-1), 4.5-4.64 (m, 1H, H-2), 5.06-5.18 (m, 1H, H-5), 7.20-7.3, 7.56-7.7 (m, 4H each, Ar—H).

Workup

  1. washwashed with aqueous CuSO4 solution (2×25 mL)
  2. dry with materialOrganic layer was dried (Na2SO4)
  3. customevaporated
  4. custompurified by chromatography (Si-gel, 15% EtOAc-hexane)
  5. washfirst eluted

Sources & evidence

ORD record
ord-62d4ad8adad24a108e7c066bd7a10609
Source dataset
uspto-grants-2003_04
Patent number
US06541647B2

Reaction notes

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