Diastereoselective Oxidative Cross-Coupling Reactions of Chiral Alkylbenzenes with Arenes and Silyl Nucleophiles

Abstract

Chiral di- and trimethoxysubstituted alkylbenzenes underwent oxidative cross-dehydrogenative coupling reactions with arenes and related oxidative coupling reactions with silyl nucleophiles in moderate to good yields (41–99%) and with significant diastereoselectivities (dr = 71:29 to >95:5).

Key words

carbocation - diastereoselectivity - electrophilic aromatic substitution - oxidation - stereoselective synthesis

• References and Notes


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For additional examples for FeCl₂-catalyzed benzylic DDQ oxidation, see refs. 4b,6f and:
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• 12 General Experimental Procedure for FeCl₂-Catalyzed, DDQ-Mediated Cross-Coupling Reactions To a solution of the substrate 3 (200 μmol, 1.00 equiv), nucleophile (800 μmol, 4.00 equiv), FeCl₂ (40 μmol, 0.20 equiv), and MeNO₂ (c 100 mM) in a flame-dried flask was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (260 μmol, 1.30 equiv) at r.t. After 1 h the solvent was removed under reduced pressure, and the crude mixture was purified by flash column chromatography (silica gel; pentane–EtOAc, 40:1) to afford the product.
• 13 General Experimental Procedure for DDQ-Mediated Cross-Coupling Reactions To a solution of the substrate 5 (200 μmol, 1.00 equiv), nucleophile (800 μmol, 4.00 equiv), and MeNO₂ (c 100 mM) in a flame-dried flask was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (260 μmol, 1.30 equiv) at r.t. After 1 h the solvent was removed under reduced pressure, and the crude mixture was purified by flash column chromatography (silica gel; pentane–EtOAc, 40:1) to afford the product.
• 14 Crystal Structure of 6f Colorless plates, C₂₄H₃₄O₅, crystal dimensions 0.12 × 0.13 × 0.13 mm; M _r = 402.51; monoclinic, space group P ₂1/n, a = 13.558(3), b = 11.365(2), c = 15.410(3) Å, β = 112.740(6)°, V = 2189.9(7) ų, Z = 4, λ(Mo Kα) = 0.71073 Å, μ = 0.084 mm^–1, ρ _calcd = 1.221 g cm^–3, T = 123(2) K, F (000) = 872, angle range θ = 1.70–23.26°; collected data: 16558; independent data [I _o > 2σ(I _o)/all data/R _int]: 1913/3089/0.1067; data/restraints/parameter: 3089/0/272; R1 [I _o > 2σ(I _o)/all data]: 0.0816/0.1330; wR2 [I _o > 2σ(I _o)/ all data]: 0.1855/0.2073; GOF = 1.049; Δρ _max/min: 0.861/–0.271 eÅ^–3. CCDC-1016616. For more details, see the Supporting Information.

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