Triphenylphosphine → HCID 9913593, compound

HRID 253761Notes

Reaction equation

HRID 253761 reaction equation
[N:1]([C@H:4]1[C@H:19](O)[CH2:18][C@@H:17](/[C:21](/[CH3:29])=[CH:22]/[C:23]2[N:24]=[C:25]([CH3:28])[S:26][CH:27]=2)[O:16][C:15](=[O:30])[CH2:14][C@H:13]([OH:31])[C:12]([CH3:33])([CH3:32])[C:11](=[O:34])[C@H:10]([CH3:35])[C@@H:9]([OH:36])[C@@H:8]([CH3:37])[CH2:7][CH2:6][CH2:5]1)=[N+]=[N-].N([C@H]1C[C@@H](/C(/C)=C/C2N=C(C)SC=2)OC(=O)C[C@H](O)C(C)(C)C(=O)[C@H](C)[C@@H](O)[C@@H](C)CCC[C@@H]1O)=[N+]=[N-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(#N)C>[OH:31][C@@H:13]1[C:12]([CH3:33])([CH3:32])[C:11](=[O:34])[C@H:10]([CH3:35])[C@@H:9]([OH:36])[C@@H:8]([CH3:37])[CH2:7][CH2:6][CH2:5][C@@H:4]2[C@@H:19]([NH:1]2)[CH2:18][C@@H:17](/[C:21](/[CH3:29])=[CH:22]/[C:23]2[N:24]=[C:25]([CH3:28])[S:26][CH:27]=2)[O:16][C:15](=[O:30])[CH2:14]1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 9850110HCID 9850110, compoundHCID 11364651HCID 11364651, compound

Product 1

HCID 9913593HCID 9913593, compoundYield 46%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
30 °C

Procedure

To a stirred solution of (4S,7R,8S,9S,13R,14R,16S)-13-Azido-4,8,14-trihydroxy-5,5,7,9-tetramethyl-16-((E)-1-(2-methylthiazol-4-yl)prop-1-en-2-yl)oxacyclohexadecane-2,6-dione and (4S,7R,8S,9S,13S,14S,16S)-14-Azido-4,8,13-trihydroxy-5,5,7,9-tetramethyl-16-((E)-1-(2-methylthiazol-4-yl)prop-1-en-2-yl)oxacyclohexadecane-2,6-dione mixture (12.8 g, 23.85 mmol) in anhydrous acetonitrile (90 mL) was added triphenylphosphine (9.48 g, 35.77 mmol) under nitrogen atmosphere. The clear solution was stirred at 20-40° C. for 19-40 h. The reaction mixture was cooled to 0-5° C. for 3-4 h and filtered the product. The cake was washed with heptane (64 mL) and dried at 40° C. under reduced pressure for 15-18 h to give (1S,3S,7S,10R,11S,12S16R)-7,11-dihydroxy-8,8,10,12-tetramethyl-3-((E)-1-(2-methylthiazol-4-yl)prop-1-en-2-yl)-4-oxa-17-azabicyclo(14.1.0)heptadecane-5,9-dione as a white solid (5.41 g, 46%). LC-MS: Phenomenex Luna C8(2) column: 3 μm, 4.6×50 mm. Gradient: 15 min, 0% B to 100% B in 10 min, then 100% B for 5 min. Mobile phases: A=0.01 M NH4OAc in CH3CN/H2O 5:95; B=0.01 M NH4OAc in CH3CN/H2O 95:5. Flow rate: 3.0 mL/min. Wavelength: UV 250 nm. Retention time=4.43 min. MS (ESI) (M+H)+=493.68

Workup

  1. temperatureThe reaction mixture was cooled to 0-5° C. for 3-4 h
  2. filtrationfiltered the product
  3. washThe cake was washed with heptane (64 mL)
  4. customdried at 40° C. under reduced pressure for 15-18 h

Sources & evidence

ORD record
ord-7d063a67200c4823a074f68f39ad2e3e
Source dataset
uspto-grants-2011_01
Patent number
US07872145B2

Reaction notes

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