Chelation-Assisted C–H and C–C Bond Activation of Allylic Alcohols by a Rh(I) Catalyst under Microwave Irradiation

Published as part of the Cluster C–C Activation

Abstract

Chelation-assisted Rh(I)-catalyzed ketone synthesis from allylic alcohols and alkenes through C–H and C–C bond activations under microwave irradiation was developed. Aldimine is formed via olefin isomerization of allyl alcohol under Rh(I) catalysis and condensation with 2-amino-3-picoline, followed by continuous C–H and C–C bond activations to produce a dialkyl ketone. The addition of piperidine accelerates the reaction rate by promoting aldimine formation under microwave conditions.

Key words

rhodium - transition metals - hydroacylation - C–C bond activation - chelation assistance - microwave irradiation

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• 10 Typical Procedure for the Rh(I)-Catalyzed Hydroacylation with Allyl Alcohol through C–H and C–C Bond ActivationTo a 10 mL thick-walled Pyrex tube were added allyl alcohol (1a, 13.6 μL, 0.2 mmol), norbornene (2a, 113.0 mg, 1.2 mmol), [Rh(C₂H₄)₂Cl]₂(3, 3.9 mg, 0.01 mmol), 2-amino-3-picoline (6, 20.2 μL, 0.2 mmol), and tricyclohexylphosphine (4, 16.8 mg, 0.06 mmol), and piperidine (5, 4.0 μL, 0.04 mmol). The reaction vessel was capped with a Teflon septum and installed in a CEM Discover microwave reactor. The reaction was carried out with internal magnetic stirring at 200 °C under microwave irradiation. After cooling, the reaction mixture was filtered through a short column filled with silica and washed with CH₂Cl₂ and ethyl acetate. The filtrate was analyzed by GC-MS and determined to be 93% of dinorbornyl ketone (7a) and 7% of norbornyl 3-propanone (8a).
• 11 Synthesis of N,N′-Bis(3-methylpyridin-2-yl)propane-1,1-diamine (10)Propionaldehyde (9a, 500 mg, 8.60 mmol) was added to 2-amino-3-picoline (6, 1.73 mL, 17.2 mmol) and 4 Å MS at room temperature. When the mixture was stirred at room temperature for 12 h, a pale yellow solid formed. It was dissolved in methylene chloride and filtered. The resulting solution was concentrated and then re-crystallized from a methylene chloride/hexane mixture, then filtered and dried in vacuo to give the aminal 10 as white solid (1.79 g, 81%). ¹H NMR (400 MHZ, CDCl₃): δ = 7.97 (d, J = 4.0 Hz, 2 H), 7.16 (d, J = 6.8 Hz, 2 H), 6.49 (dd, J = 5.2, 7.2 Hz, 2 H), 5.73 (d, J = 5.73 Hz, 2 H, NH), 5.57–5.53 (m, 1 H), 2.28–2.25 (m, 2 H), 2.02 (s, 6 H), 1.01 (t, J = 7.2 Hz, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 156.8, 145.1, 137.2, 117.9, 113.1, 63.8, 27.6, 17.4, 11.4 ppm. IR (CH₂Cl₂): 3415, 3379, 2966, 2947, 2875, 1598, 1581, 1506, 1487, 1463, 1413, 1334, 1325, 1282, 1188, 1149, 1114, 1031, 779 cm^–1. Aminal 10 is determined as aldimine 9b in HRMS. ESI-HRMS: m/z calcd for C₉H₁₂N₂148.1000; found: 149.1050 [M + H⁺].