Tri-o-tolylphosphine → 5'-Ethenylspiro[1-azabicyclo[2.2.2]octane-3,2'(3'H)-furo[2,3-b]pyrdine]

HRID 49620Notes

Reaction equation

HRID 49620 reaction equation
Br[C:2]1[CH:3]=[C:4]2[CH2:10][C:9]3([CH:15]4[CH2:16][CH2:17][N:12]([CH2:13][CH2:14]4)[CH2:11]3)[O:8][C:5]2=[N:6][CH:7]=1.[C:18]1(C)C=CC=C[C:19]=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[Cl-].[Li+].C(C([SnH3])=C(CCCC)CCCC)CCC>COCCOC.C(Cl)(Cl)Cl.CO>[CH:18]([C:2]1[CH:3]=[C:4]2[CH2:10][C:9]3([CH:15]4[CH2:16][CH2:17][N:12]([CH2:13][CH2:14]4)[CH2:11]3)[O:8][C:5]2=[N:6][CH:7]=1)=[CH2:19]

Participants

8

Reactant 4

HCID 80271Tri-o-tolylphosphineHCID 433294Lithium ChlorideHCID 103571335'-bromospiro[1-azabicyclo[2.2.2]octane-3,2'(3'H)-furo[2,3-b]pyridine]HCID 21115800Tri(butyl)vinylstannane

Product 1

HCID 220458645'-Ethenylspiro[1-azabicyclo[2.2.2]octane-3,2'(3'H)-furo[2,3-b]pyrdine]Yield 186.9%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6212ChloroformSolvent2×HCID 80711,2-DimethoxyethaneSolvent

Procedure

A solution containing 5′-bromospiro[1-azabicyclo[2.2.2] octane-3,2′(3′H)-furo[2,3-b]pyridine] (150 mg, 0.508 mmol), tris(dibenzylidineacetone)dipalladium (0) (22 mg, 0.024 mmol), tri(o-tolyl)phosphine (63 mg, 0.206 mmol), lithium chloride (103 mg, 2.43 mmol), and tri-n-butylvinylstannane (188 mg, 0.592 mmol) in 1,2-dimethoxyethane (10 ml) was heated under reflux overnight. The solution was evaporated, and the residue was taken up in chloroform and filtered. The filtrate was evaporated then purified by HPLC using a gradient of 0-25% 1:1:2 7M methanolic ammonia:methanol:chloroform and chloroform to obtain the title compound (93 mg, 0.385 mmol, 76%) as a pale solid: electrospray MS (m/z, relative intensity) 243 ([MH]+, 100).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux overnight
  3. customThe solution was evaporated
  4. filtrationfiltered
  5. customThe filtrate was evaporated
  6. customthen purified by HPLC

Sources & evidence

ORD record
ord-30357bd076284d769aa2562d6bd183b6
Source dataset
uspto-grants-2004_03
Patent number
US06706878B2

Reaction notes

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