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 931680Notes

Reaction equation

C(N(CC)CC)C.[CH3:8][C:9]1([CH3:16])[C:13]([CH3:15])([CH3:14])[O:12][BH:11][O:10]1.[CH2:17]([N:21]1[CH2:26][C:25]2([CH2:31][CH2:30][N:29]([C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])[CH2:28][CH2:27]2)[CH2:24][CH2:23][CH2:22]1)[CH2:18][C:19]#[CH:20]>ClCCl.[Cl-].[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Zr+2]>[CH3:8][C:9]1([CH3:16])[C:13]([CH3:15])([CH3:14])[O:12][B:11](/[CH:20]=[CH:19]/[CH2:18][CH2:17][N:21]2[CH2:26][C:25]3([CH2:27][CH2:28][N:29]([C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])[CH2:30][CH2:31]3)[CH2:24][CH2:23][CH2:22]2)[O:10]1

Participants

Conditions

Temperature: 65 °C

Procedure

Triethylamine (5.62 mmoles; 0.783 mL), 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.56 mL, 59.0 mmol) and zirconocene chloride (1.45 g, 5.62 mmoles) are added to tert-butyl 4-but-3-ynyl-4,9-diazaspiro[5.5]undecane-9-carboxylate (17.21 g, 56.16 mmoles). The resulting mixture is heated to 65° C. for 3.5 hours. The mixture is cooled and dissolved in dichloromethane (150 mL). The resulting solution is passed through a ˜4 cm thick pad of silica gel, eluting with dichloromethane (2×200 mL). The filtrate is concentrated under reduced pressure to give the title compound (21.2 g, 87% yield). 1H NMR (300.11 MHz, CDCl3): δ 6.65-6.55 (m, 1H), 5.49-5.43 (m, 1H), 3.42-3.29 (m, 4H), 2.40-2.27 (m, 6H), 2.25-2.08 (m, 2H), 1.70-1.13 (m, 29H).

Workup

temperatureThe mixture is cooled
washeluting with dichloromethane (2×200 mL)
concentrationThe filtrate is concentrated under reduced pressure

Sources & evidence

ORD record: ord-200a47a2b3884493b9b0bd1fb14713a3
Source dataset: uspto-grants-2016_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09296775B2

Reaction notes

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