Palladium-Catalyzed Direct Amination of Allylic Alcohols at Room Temperature

Abstract

A palladium complex ligated with Xantphos has been identified as an efficient catalyst for the catalytic amination of allylic alcohols, which allows the direct amination of allylic alcohols with amines to proceed at room temperature in the absence of additives. The method is compatible with a variety of functional groups and can be used to prepare a wide range of linear allylic amines in good to excellent yields with high stereoselectivities.

Key words

palladium - amination - allylic alcohols - room temperature - additive-free

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• 7 General Procedure for Amination of Allylic Alcohols: Allylic alcohols 1 (0.4 mmol), Pd(Xantphos)Cl₂ (0.02 mmol, 5 mol%), amines 2 (0.6 mmol) and 2-PrOH (1.5 mL) were added to a 25-mL flame-dried Young-type tube under a nitrogen atmosphere. The mixture was stirred at r.t. for 12 h. After the mixture was concentrated under reduced pressure, the residue was purified by flash column chromatography on silica gel and eluted with EtOAc–PE (1:100 to 1:1) to afford the desired product 3. Selected spectral data: Compound 3aa: ¹H NMR (400 MHz, CDCl₃): δ = 7.07–7.31 (m, 15 H), 6.41 (d, J = 16.0 Hz, 1 H), 6.17–6.24 (m, 1 H), 3.53 (s, 4 H), 3.12 (d, J = 5.6 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 138.6, 136.1, 131.4, 127.7, 127.5, 127.2, 126.7, 126.2, 125.8, 125.2, 56.9, 54.7. HRMS (ESI): m/z [M + H] calcd for C₂₃H₂₄N: 314.1903; found: 314.1909. Compound 3ad: ¹H NMR (400 MHz, CDCl₃): δ = 7.56 (d, J = 6.8 Hz, 1 H), 7.13–7.42 (m, 11 H), 6.94–6.97 (m, 1 H), 6.80 (d, J = 7.6 Hz, 1 H), 6.52 (d, J = 16.0 Hz, 1 H), 6.29–6.36 (m, 1 H), 3.76 (s, 3 H), 3.66–3.68 (m, 4 H), 3.25 (d, J = 6.4 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 157.7, 140.0, 137.4, 132.3, 129.9, 128.9, 128.6, 128.3, 127.9, 127.8, 127.4, 126.9, 126.4, 120.6, 110.3, 58.4, 56.3, 55.4, 51.5. HRMS (ESI): m/z [M + H] calcd for C₂₄H₂₆N: 344.2009; found: 344.2004.
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