Triethylamine → tert-butyl 4-[(E)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-3-enyl]-4,9-diazaspiro[5.5]undecane-9-carboxylate

HRID 1625939Notes

Reaction equation

[CH2:1]([N:5]1[CH2:22][CH2:21][CH2:20][C:7]2([CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH2:8]2)[CH2:6]1)[CH2:2][C:3]#[CH:4].C(N(CC)CC)C.[CH3:30][C:31]1([CH3:38])[C:35]([CH3:37])([CH3:36])[O:34][BH:33][O:32]1>[Cl-].[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Zr+2].ClCCl>[CH3:30][C:31]1([CH3:38])[C:35]([CH3:37])([CH3:36])[O:34][B:33](/[CH:4]=[CH:3]/[CH2:2][CH2:1][N:5]2[CH2:6][C:7]3([CH2:8][CH2:9][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:17])[CH3:18])=[O:14])[CH2:11][CH2:12]3)[CH2:20][CH2:21][CH2:22]2)[O:32]1

Participants

Conditions

Temperature: 65 °C

Procedure

Tert-butyl 8-but-3-ynyl-3,8-diazaspiro[5.5]undecane-3-carboxylate (129.00 g, 420.95 mmoles), triethylamine (5.87 mL, 42.10 mmoles), and zirconocene chloride (10.86 g, 42.10 mmoles) are combined. To this is added 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (64.13 mL 442.00 mmoles) via syringe. The reaction is then heated to 65° C. and stirred at this temperature for 24 hours. The heat is turned off and the reaction allowed to stir at ambient temperature for a further 24 hours. Dichloromethane (500 mL) is added and the resulting solution is filtered through a 10 cm pad of silica eluting with 20% ethyl acetate in dichloromethane (3×500 mL). The filtrate is concentrated under reduced pressure to provide the title compound (163.5 g; Yield 89%). Mass spectrum (m/z): 435.35 (M+1).

Workup

stirringto stir at ambient temperature for a further 24 hours
filtrationthe resulting solution is filtered through a 10 cm pad of silica eluting with 20% ethyl acetate in dichloromethane (3×500 mL)
concentrationThe filtrate is concentrated under reduced pressure

Sources & evidence

ORD record: ord-efd15f4813ee4a39a86a0f80f6237256
Source dataset: uspto-grants-2014_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08785404B2

Reaction notes

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