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DOI: 10.1055/s-0031-1290365
Synthesis of Allenes via Nickel-Catalyzed Cross-Coupling Reaction of Propargylic Bromides with Grignard Reagents
Publication History
Publication Date:
24 February 2012 (online)

Abstract
We describe a convenient method for the synthesis of terminal allenes from cross-coupling of propargylic bromide with Grignard reagent. The reaction of propargylic bromide with 1.2 equivalents of Grignard reagent mediated by Ni(acac)2 (2 mol%) and Ph3P (4 mol%) in THF may produce terminal allenes in good yields and high regioselectivities at room temperature.
Key words
allenes - nickel - propargylic bromide - Grignard reagent - cross-coupling
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References and Notes
General Procedure
for the Cross-Coupling of Propargylic Bromide with Grignard Reagent
Under
an atmosphere of nitrogen, Ni(acac)2 (5.12 mg, 0.02 mmol),
Ph3P (0.04 mmol), and THF (2 mL) were mixed in a Schlenk
flask. Shortly afterwards, aryl or alkyl Grignard reagent (1.2 mmol)
was added, and subsequently the proparglic bromide was added. Then
the reaction mixture was stirred at r.t. for 4-6 h. After
completion of the reaction, the mixture was diluted with H2O
(15 mL) and extracted with Et2O (3 × 15
mL). The combined organic layers were dried over anhydrous Na2SO4,
filtered, and evaporated in vacuum. The residue was subjected to
flash column chromatography on silica gel (hexane or EtOAc-hexane, 100:1)
to afford the corresponding allene products 3. Allenylbenzene (3aa):¹³e colorless
oil; ¹H NMR (400 MHz, CDCl3): δ = 7.31-7.19
(m, 5 H), 6.17 (t, J = 6.8 Hz, 1 H), 5.16
(d, J = 6.8 Hz, 2 H). ¹³C {¹H} NMR
(100 MHz, CDCl3): δ = 209.8, 133.9,
128.6, 126.9, 126.7, 93.9, 78.7. HRMS: m/z calcd for C9H8:
116.0626; found: 116.0637 [M]+.