Divergent Nickel-Catalysed Ring-Opening–Functionalisation of Cyclobutanone Oximes with Organozincs

Published as part of the Cluster 9^th Pacific Symposium on Radical Chemistry

Abstract

The development of a nickel-catalysed strategy for the remote alkylation, arylation, vinylation and alkynylation of nitriles is presented. The methodology uses electron-poor O-Ar cyclic oximes and organozincs as coupling partners. This redox process proceeds through the generation of an iminyl radical and its following ring-opening reaction.

Key words

radical ring-opening - nickel catalysis - nitrogen radicals - C–C bond formation - alkylation - arylation - vinylation - alkynylation

• References and Notes


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• 12 Products 2, 5–20; General Procedure An oven-dried microwave vial equipped with a stirring bar was charged with the aryl oxime (0.05 mmol, 1.0 equiv) and dtbpy·NiBr₂ (20 mol%). The vial was sealed, evacuated and refilled with N₂ (3×). DMF was added followed by the organozinc (0.1 mmol, 1.0 equiv) as a solution in THF (DMF–THF 1:1, 0.05 M). The reaction was stirred at room temperature for 16 h and then it was filtered through a silica plug by eluting with EtOAc. The solution was washed with H₂O (3×), and brine (1×), dried (MgSO₄), filtered and evaporated. Purification by column chromatography on silica gel gave the corresponding product. 7,11-Dimethyldodecanenitrile (5) Following the general procedure, 1 gave 5 (13 mg, 61%) as a colorless oil; R_f 0.90 (PE–EtOAc, 8:2). ¹H NMR (500 MHz, CDCl₃): δ = 2.33 (t, J = 7.1 Hz, 2 H), 1.66 (quin, J = 7.3 Hz, 2 H), 1.59–1.48 (m, 1 H), 1.47–1.33 (m, 4 H), 1.33–1.18 (m, 5 H), 1.17–0.99 (m, 4 H), 0.92–0.75 (m, 9 H). ¹³C NMR (126 MHz, CDCl₃): δ = 120.0, 39.5, 37.4, 36.8, 32.8, 29.2, 28.1, 26.4, 25.6, 24.9, 22.9, 22.8, 19.8, 17.3. HRMS (ASAP): m/z [M + H]⁺ calcd for C₁₄H₂₈N: 210.2216; found: 210.2212. tert-Butyl-4-(cyanomethyl)-4-(prop-2-yn-1-yl)piperidine-1-carboxylate (20) Following the general procedure, 1 gave 20 (16 mg, 54%) as a colorless oil; R_f 0.50 (PE–EtOAc, 7:3). ¹H NMR (500 MHz, CDCl₃): δ = 3.57–3.44 (m, 2 H), 3.37–3.25 (m, 2 H), 2.53 (s, 2 H), 2.41 (d, J = 2.7 Hz, 2 H), 2.10 (t, J = 2.6 Hz, 1 H), 1.71–1.59 (m, 4 H), 1.46 (s, 9 H). ¹³C NMR (126 MHz, CDCl₃): δ = 154.8, 117.3, 80.1, 79.1, 72.6, 34.8, 33.5, 31.1, 28.6, 26.6, 21.2. HRMS (ASAP): m/z [M + H]⁺ calcd for C₁₅H₂₃N₂O₂: 263.1754; found: 263.1749.
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