2,2'-Bipyridine → HCID 67215903, compound

HRID 1936191Notes

Reaction equation

HRID 1936191 reaction equation
[Li:1].[C:2]([C:6]1[CH:11]=[CH:10][C:9]([C:12]2[CH:17]=[CH:16][C:15]([C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:14][CH:13]=2)=[CH:8][CH:7]=1)([CH3:5])([CH3:4])[CH3:3].N1C=CC=CC=1C1C=CC=CN=1.[Li]CCCC>O1CCCC1>[C:18]([C:15]1[CH:16]=[CH:17][C:12]([C:9]2[CH:8]=[CH:7][C:6]([C:2]([CH3:5])([CH3:4])[CH3:3])=[CH:11][CH:10]=2)=[CH:13][CH:14]=1)([CH3:21])([CH3:20])[CH3:19].[Li:1]

Participants

6

Reactant 4

HCID 14742,2'-BipyridineHCID 741954,4'-Bis(1,1-dimethylethyl)-1,1'-biphenylHCID 3028194LithiumHCID 178418339Butyllithium

Product 1

HCID 67215903HCID 67215903, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Lithium wire (1% Na) (68 mg, 9.7 mg-atom) was added in 0.3-cm pieces to a stirred, cooled (0° C. internal) solution of 4,4′-di-t-butylbiphenyl (2.66 g, 10.0 mmol) and 5 mg of 2,2′-bipyridyl in 20 mL of dry tetrahydrofuran (THF) under argon. The mixture was titrated to a red endpoint with n-BuLi (2.5 M in hexane, 0.12 mL) and stirred for 15 hours to form a deep blue-green solution of lithium 4,4′-di-t-butylbiphenyl. The solution was cooled to −45° C. (internal), and a solution of (R)-1-(3-chloro-1-cyclohexyl)propyl(1-ethoxyethyl)ether (1.12 g, 4.5 mmol) in 9.0 mL of dry hexane was added dropwise. After 5 minutes, a solution of 0.25 M lithium (2-thienyl)cyanocuprate in THF (20 mL) was added dropwise. After 10 minutes, a solution of (R)-2-((diethylamino)methyl)-4-(t-butyldimethylsiloxy)-2-cyclopentenone (1.12 g, 3.77 mmol) in 20 mL of dry THF was added dropwise. The solution was allowed to warm to −20° C. and was quenched into a rapidly stirred mixture of diethyl ether and saturated aqueous NH4Cl. After four hours, the layers were separated and the aqueous solution was extracted with ethyl acetate. The combined organic solutions were dried (MgSO4), filtered and concentrated and the crude product was purified by chromatography on silica to give 0.95 g (57.5%) of (3R,4R)-2-methylene-3-[(3′R)-3′-(1-ethoxy)ethoxy)-3′-cyclohexyl-1′-propyl]-4-(t-butyldimethylsiloxy)cyclopentan-1-one. NMR (CDCl3) δ0.06 (s, 3H), 0.08 (s, 3H), 0.87 (s, 9H), 0.8-1.9 (m, 15H), 1.17 and 1.20 (2 overlapping t, J=7, 3H), 1.29 and 1.30 (2 overlapping d, J=5.3, 3H), 2.30 (A of ABX, Jab=18.0, Jax=4.6, 1H), 2.62 (B of ABX, Jab=17.8, Jbx=5.8, 1H), 2.65 (br s, 1H), 3.30 (br q, J=4, 1H), 3.55 (m, J=6, 2H), 4.12 (pent, J=5.2, 1H), 4.68 (2 overlapping q, J=5.2, 1H), 5.29, 5.32 (both s, 2:3 ratio, total 1H), 6.08 (s, 1H).

Sources & evidence

ORD record
ord-cf5d37bedd3d4860b730a1e3df84a462
Source dataset
uspto-grants-2002_05
Patent number
US06388128B1

Reaction notes

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