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DOI: 10.1055/s-0036-1590890
Sequential O-Arylation/Lanthanide(III)-Catalyzed [3,3]-Sigmatropic Rearrangement of Bromo-Substituted Allylic Alcohols
We are grateful for financial support by Takeda Pharmaceutical Company (TPC) Ltd. and by the Natural Sciences and Engineering Research Council (NSERC) of Canada for a Discovery Grant to R.A.B and Alexander Graham Bell Canada Graduate Scholarships M and D3 to T.R.R.Publikationsverlauf
Received: 03. Juli 2017
Accepted after revision: 28. Juli 2017
Publikationsdatum:
25. August 2017 (online)
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Dedicated to the Cardinal Chemist, the inimitable Prof. Victor Snieckus, on the occasion of his 80th birthday
Abstract
Lanthanide(III)-catalyzed aryl-Claisen rearrangement of substrates bearing halo-substituted allyl groups, specifically 2-bromoallyl aryl ethers, afford ortho-2-bromoallylphenols. Aryl ether substrates were synthesized from brominated allylic alcohols via Mitsunobu reaction, Cu(II)-catalyzed arylation using potassium aryltrifluoroborate salts, or SNAr reaction. Aryl-Claisen rearrangements proceeded in moderate to excellent yields using Eu(III) catalysis. The alkenylbromide functionality remains intact, illustrating the compatibility of synthetically important alkenylhalides during C–O/C–C σ-bond migration processes. Subsequent derivatization of the ortho-2-bromoallylphenol products through O-alkylation or C-arylation/alkenylation via Suzuki–Miyaura cross-coupling demonstrate the potential to access densely-functionalized molecules.
Key words
aryl-Claisen [3,3]-sigmatropic rearrangement - alkenylbromide - arylation - organotrifluoroborate salt - lanthanide catalysis - phenols - Suzuki–Miyaura reaction - Chan–Lam–Evans arylationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590890.
- Supporting Information
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References and Notes
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- 17 General Procedure for O-Aryl 2-Bromoallylic Ether Synthesis via Cu(II)-Catalyzed Arylation A suspension of ArBF3K, Cu(OAc)2·H2O (10 mol%), DMAP (20 mol%), and powdered 4Å MS in CH2Cl2 was stirred at rt for 5 min. To this suspension was added alcohol 6. The mixture was stirred at rt for 60–72 h under an O2 atmosphere. Subsequently, the mixture was filtered through a pad of Celite, and the filtrate was concentrated in vacuo. The resultant crude mixture was purified using flash column chromatography on silica gel to afford aryl ether 7. Example Reaction of 6a (0.250 g, 1.4 mmol) with 4-FC6H4BF3K (0.601 g (95% purity), 2.8 mmol) using the general procedure afforded 7c (0.171 g, 45%) as a clear oil. Analytical Data for Compound 7c Rf = 0.43 (5% EtOAc/hexanes). IR (thin film): νmax = 3073, 3051, 2945, 2934, 2866, 2834, 1647, 1601, 1505, 1439, 1368, 1240, 1202, 1090, 1057, 999, 974, 914, 826, 785, 725 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.00–6.94 (4 H, m), 6.38 (1 H, dd, J = 5.0, 3.0 Hz), 4.64–4.62 (1 H, m), 2.27–2.19 (1 H, m), 2.14–2.04 (1 H, m), 1.86–1.74 (2 H, m), 1.70–1.61 (1 H, m). 13C NMR (100 MHz, CDCl3): δ = 158.0 (d, 1 J CF = 239.5 Hz), 154.4 (d, 4 J CF = 2.5 Hz), 135.0, 121.2, 118.6 (d, 3 J CF = 8.0 Hz), 116.1 (d, 2 J CF = 23.0 Hz), 78.0, 29.3, 28.0, 16.8. 19F NMR (376 MHz, CDCl3): δ = –123.41 (m). LRMS (EI+): m/z (rel. intensity) = 272 (5), 270 (5) [M]+, 161 (14), 160 (93), 159 (17), 158 (94), 112 (78), 79 (100). HRMS (EI+): m/z calcd for C12H12OFBr [M]+: 270.0056; found: 270.0061.
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See, for example:
Isolated examples of aryl-Claisen [3,3]-sigmatropic rearrangement of simple acyclic 2-bromoallyl aryl ethers have been reported, see: