Tributylstannane → HCID 71237312, compound

HRID 2280710Notes

Reaction equation

HRID 2280710 reaction equation
Br[C@@H:2]1[C@@H:8]([OH:9])[CH2:7][CH2:6][CH2:5][CH2:4][C@H:3]1[N:10]1[C:18](=[O:19])[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11]1=[O:20].C([SnH](CCCC)CCCC)CCC.N(C(C)(C)C#N)=NC(C)(C)C#N>C1(C)C=CC=CC=1.CO>[OH:9][C@H:8]1[CH2:7][CH2:6][CH2:5][CH2:4][C@@H:3]([N:10]2[C:11](=[O:20])[C:12]3[C:17](=[CH:16][CH:15]=[CH:14][CH:13]=3)[C:18]2=[O:19])[CH2:2]1

Participants

6

Reactant 3

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 86676335HCID 86676335, compound

Product 1

HCID 71237312HCID 71237312, compoundYield 81%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 1140TolueneSolvent

Procedure

To a solution of 2-((1R,2S,3S)-2-bromo-3-hydroxycycloheptyl)isoindoline-1,3-dione (4.2 g, 12.42 mmol) in toluene (69 mL) and methanol (6.9 mL) was added tributyltin hydride (4.34 mL, 16.14 mmol) via syringe over 10 minutes under nitrogen followed by 2,2′-azobis(2-methylpropanenitrile) (0.204 g, 1.242 mmol) in one portion. The reaction was then heated to reflux overnight under a nitrogen atmosphere. The reaction mixture was concentrated to dryness under reduced pressure to afford a residue that was purified by silica gel chromatography (0-50% ethyl acetate in hexanes). Fractions containing the desired product were concentrated under reduced pressure to afford the title compound (2.6 g, 10.03 mmol, 81% yield) as a solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.72-7.98 (m, 4H), 4.58 (d, J=4.29 Hz, 1H), 4.14 (br. s., 1H), 3.67 (dt, J=6.25, 3.90 Hz, 1H), 2.24-2.40 (m, 1H), 2.04-2.19 (m, 1H), 1.81-1.95 (m, 2H), 1.39-1.80 (m, 6H). MS (ESI) m/z 259.9 [M+H]+.

Workup

  1. temperatureThe reaction was then heated
  2. temperatureto reflux overnight under a nitrogen atmosphere
  3. concentrationThe reaction mixture was concentrated to dryness under reduced pressure
  4. customto afford a residue that
  5. customwas purified by silica gel chromatography (0-50% ethyl acetate in hexanes)
  6. additionFractions containing the desired product
  7. concentrationwere concentrated under reduced pressure

Sources & evidence

ORD record
ord-6775544ab0b34a2199b522c94ce8c11b
Source dataset
uspto-grants-2015_09
Patent number
US09139534B2

Reaction notes

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