Methanol → HCID 118342875, compound

HRID 2202713Notes

Reaction equation

HRID 2202713 reaction equation
[Cl:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Cl:20])[C:7]=1[CH2:8][C@H:9]1[CH2:13][C:12]([CH2:17][CH:18]=[CH2:19])([CH2:14]C=C)[CH2:11][NH:10]1.CO>Cl[Ru](=C1N(C2C(C)=CC(C)=CC=2C)CCN1C1C(C)=CC(C)=CC=1C)(Cl)(=CC1C=CC=CC=1)[P](C1CCCCC1)(C1CCCCC1)C1CCCCC1.C(Cl)Cl>[Cl:20][C:6]1[CH:5]=[N:4][CH:3]=[C:2]([Cl:1])[C:7]=1[CH2:8][C@H:9]1[CH2:13][C:12]2([CH2:14][CH:19]=[CH:18][CH2:17]2)[CH2:11][NH:10]1

Participants

5

Reactant 2

HCID 887MethanolHCID 118342944HCID 118342944, compound

Product 1

HCID 118342875HCID 118342875, compoundYield 35.5%

Reagents, catalysts & solvents 2

HCID 178425456HCID 178425456, compoundCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
40 °C

Procedure

A mixture (R)-3,5-dichloro-4((4,4-diallylpyrrolidin-2-yl)methyl)pyridine (3.1 g, 9.96 mmol) and grubbs catalyst 2nd generation (1.691 g, 1.992 mmol) in DCM (996 ml). The mixture was stirred at 40° C. for 20 h. The mixture was concentrated and absorbed onto a plug of silica gel and purified by chromatography through a Biotage column (100 g), eluting with a gradient of 1% to 50% 1 M NH3.MeOH in DCM, to provide (R)-3-((3,5-dichloropyridin-4-yl)methyl)-2-azaspiro[4.4]non-7-ene (1.0 g, 3.53 mmol, 35.5% yield) as dark-brown oil. 1H NMR (400 MHz, CDCl3) δ 8.45 (s, 2H), 5.61-5.72 (m, 2H), 3.69-3.82 (m, 1H), 3.25 (br. s., 2H), 3.05 (d, J=10.47 Hz, 1H), 2.89-2.97 (m, 1H), 2.47 (br. s., 2H), 2.23-2.37 (m, 2H), 1.93 (dd, J=6.84, 12.59 Hz, 1H), 1.69-1.82 (m, 1H); LCMS (ESI) m/z 283.0 (M+H)+.

Workup

  1. concentrationThe mixture was concentrated
  2. customabsorbed onto a plug of silica gel
  3. custompurified by chromatography through a Biotage column (100 g)
  4. washeluting with a gradient of 1% to 50% 1 M NH3

Sources & evidence

ORD record
ord-912a0bb2f36e4950b04d49a83b58458b
Source dataset
uspto-grants-2016_06
Patent number
US09365522B2

Reaction notes

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