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Dimethylformamide → (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carbonitrile

HRID 422171
Notes
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Reaction equation

HRID 422171 reaction equation
FC(F)(F)S(O[C:7]1[CH:24]=[C:23]([O:25][CH3:26])[CH:22]=[C:21]2[C:8]=1[C@@:9]1([CH3:30])[C@H:18]([CH2:19][S:20]2)[C@:17]2([CH3:27])[C@H:12]([C:13]([CH3:29])([CH3:28])[CH2:14][CH2:15][CH2:16]2)[CH2:11][CH2:10]1)(=O)=O.[CH3:33][N:34](C=O)C>CCOC(C)=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].[C-]#N.[C-]#N.[Zn+2]>[CH3:26][O:25][C:23]1[CH:22]=[C:21]2[C:8]([C@@:9]3([CH3:30])[C@H:18]([CH2:19][S:20]2)[C@:17]2([CH3:27])[C@H:12]([C:13]([CH3:29])([CH3:28])[CH2:14][CH2:15][CH2:16]2)[CH2:11][CH2:10]3)=[C:7]([C:33]#[N:34])[CH:24]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 2

HCID 6228DimethylformamideHCID 53241983(1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-yl trifluoromethanesulfonate

Product 1

HCID 58294810(1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carbonitrileYield 67%

Reagents, catalysts & solvents 4

HCID 11186
Zinc cyanide (Zn(CN)2)
Catalyst
HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)Catalyst
HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalyst
HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
150 °C

Procedure

A mixture of (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-yl trifluoromethanesulfonate (32) (0.20 g, 0.40 mmol), Pd(dba)2 (0.037 g, 0.11 mmol), dppf (0.09 g, 0.2 mmol), Zn(CN)2 (0.057 g, 0.48 mmol) in anhydrous DMF (5.0 mL) was placed in a microwave tube. The vessel was heated at 150° C. and 10 psi for 1 h. The reaction was cooled to room temperature, diluted with EtOAc and washed with water. The organic layer was concentrated to dryness. The crude product was purified by flash chromatography on silica gel (Hexanes/EtOAc, 10:1) to yield (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carbonitrile (77) (0.10 g, 67%) as a white solid.

Workup

  1. customwas placed in a microwave tube
  2. temperatureThe reaction was cooled to room temperature
  3. washwashed with water
  4. concentrationThe organic layer was concentrated to dryness
  5. customThe crude product was purified by flash chromatography on silica gel (Hexanes/EtOAc, 10:1)

Sources & evidence

ORD record
ord-8166d12d5142454bb284b4f95c4b288f
Source dataset
uspto-grants-2012_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08101605B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes