An Environmentally Friendly Synthesis of Functionalized Indanes Using Electrochemical Cyclization of ortho-Halo-Substituted Homoallyl Ethers and Esters

Sandra Olivero; Rodolphe Perriot; Elisabet Duñach; Ashvin R. Baru; Eric D. Bell; Ram S. Mohan

doi:10.1055/s-2006-948182

LETTER

An Environmentally Friendly Synthesis of Functionalized Indanes Using Electrochemical Cyclization of ortho-Halo-Substituted Homoallyl Ethers and Esters

Sandra Olivero^a, Rodolphe Perriot^a, Elisabet Duñach*^a, Ashvin R. Baru^b, Eric D. Bell^b, Ram S. Mohan*^b
^a Laboratoire des Molécules Bioactives et des Arômes, CNRS, UMR 6001, Université de Nice-Sophia Antipolis, 06108 Nice Cedex 2, France
e-Mail: dunach@unice.fr;
^b Laboratory for Environmentally Friendly Organic Synthesis, Department of Chemistry, Illinois Wesleyan University, Bloomington, IL 61701, USA
e-Mail: rmohan@iwu.edu;

Abstract

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Abstract

The electrochemical cyclization of a series of ortho-halo-substituted homoallyl ethers and esters to functionalized indanes catalyzed by Ni(II) catalyst precursors derived from Ni(cyclam)Br₂, (cyclam = 1,4,8,11-tetraazacyclotetradecane) and Ni(tmc)Br₂, (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) is reported. The starting homoallyl ethers were synthesized using either a one-pot method for allylation of aldehydes or by direct allylation of the corresponding acetals using bismuth triflate as a catalyst. The remarkably low toxicity, low cost and ease of handling of bismuth salts coupled with the mild nature of the electrochemical procedure makes this approach to indane synthesis especially environmentally friendly and attractive.

Key words

bismuth - electrochemical cyclization - homoallyl ethers - indanes - Ni(II) cyclam

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Referenzen

References and Notes

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19a

Compound 1a (Method A, 76%): ¹H NMR: δ = 1.79 (t, 3 H, J = 7.2 Hz), 2.42-2.46 (m, 2 H), 3.35-3.39 (m, 2 H), 4.72-4.73 (m, 1 H), 5.01-5.10 (m, 2 H), 5.83-5.89 (m, 1 H), 7.25-7.52 (m, 4 H). ¹³C NMR (12 peaks): δ = 14.8, 40.7, 64.1, 79.4, 116.4, 122.5, 127.1, 127.2, 128.2, 132.1, 134.2, 141.1. HRMS: m/e calcd for C₁₂H₁₅BrO: 254.0306 [M]; found: 253.0231 [M - 1].

19b

Compound 1b (Method A, 88%): ¹H NMR: δ = 2.45 (m, 2 H), 3.24 (s, 3 H), 4.65 (dd, 1 H), 5.07 (m, 2 H), 5.85 (dp, 1 H), 7.42 (m, 4 H). ¹³C NMR (11 peaks): δ = 41.0, 50.9, 81.7, 117.0, 123.1, 127.5, 127.6, 128.8, 132.6, 134.4, 140.7. HRMS: m/e calcd for C₁₁H₁₃BrO: 240.0150 [M]; found: 239.0066 [M - 1].

19c

Compound 1c (Method D, 27%): ¹H NMR: δ = 2.09 (s, 3 H), 2.55-2.60 (m, 2 H), 5.04-5.10 (t, 2 H, J = 6.43 Hz), 5.72-5.78 (m, 1 H), 6.12-6.15 (dd, 1 H, J = 7.67, 2.73 Hz), 7.09-7.54 (m, 4 H). ¹³C NMR (12 peaks): δ = 21.0, 39.5, 73.8, 118.1, 122.0, 127.2, 127.4, 129.0, 132.7, 132.9, 139.6, 169.7. HRMS: m/e calcd for C₁₂H₁₃BrO₂: 268.0099 [M]; found: 268.0098 [M - 1].

19d

Compound 1d (Method C, 27%): ¹H NMR: δ = 2.48 (t, 2 H, J = 6.9 Hz), 4.28-4.48 (dd, 2 H), 4.86 (t, 1 H, J = 6.18 Hz), 5.02-5.10 (m, 2 H), 5.81-5.94 (m, 1 H), 7.12-7.55 (m, 9 H). ¹³C NMR (15 peaks): δ = 41.2, 70.9, 79.6, 117.1, 123.1, 127.6, 127.7 (2 peaks), 127.9, 128.3, 128.9, 132.7, 134.5, 138.2, 141.0. HRMS: m/e calcd for C₁₇H₁₇BrO: 316.0463 [M]; found: 315.0381 [M - 1].

19e

Compound 1e (Method C, 77%): ¹H NMR: δ = 1.18 (t, 3 H, J = 7.18 Hz), 2.42-2.46 (m, 2 H), 3.36-3.39 (m, 2 H), 4.76-4.80 (m, 1 H), 5.00-5.10 (m, 2 H), 5.79-5.92 (m, 1 H), 7.16-7.50 (m, 4 H). ¹³C NMR (12 peaks): δ = 14.7, 40.6, 64.1, 77.1, 116.3, 126.5, 126.9, 127.8, 128.8, 132.3, 134.2, 139.6. HRMS: m/e calcd for C₁₂H₁₅ClO: 210.0811 [M]; found: 209.0740 [M - 1].

19f

Compound 1f (Method B, 81%): this compound has been reported previously. [15] The spectral data are given here. ¹H NMR: δ = 2.46 (m, 2 H), 3.22 (s, 3 H), 4.70 (dd, 1 H, J = 7.3, 4.9 Hz), 5.02 (m, 2 H), 5.86 (m, 1 H), 7.32 (m, 4 H). ¹³C NMR: (11 peaks): δ = 40.9, 56.9, 79.4, 116.9, 126.9, 127.2, 128.3, 129.3, 132.8, 134.3, 139.1.

19g

Compound 1g (Method D, 33%): this compound has been reported previously. [15] The spectral data are given here. ¹H NMR: δ = 2.09 (s, 3 H), 2.54-2.62 (m, 2 H), 5.03-5.10 (t, 2 H, J = 6.18 Hz), 5.68-5.81 (m, 1 H), 6.18-6.23 (dd, 1 H, J = 7.7, 2.5 Hz), 7.19-7.41 (m, 4 H). ¹³C NMR (12 peaks): δ = 20.9, 39.4, 71.6, 118.1, 126.8, 127.1, 128.7, 129.5, 132.0, 132.9, 137.9, 169.7.

19h

Compound 1h (Method C, 35%): ¹H NMR: δ = 2.50 (app t, 2 H), 4.38 (dd, 2 H), 4.91 (t, 1 H, J = 6.2 Hz), 5.02 (m, 1 H), 5.90 (dquar, 2 H), 7.30 (m, 9 H). ¹³C NMR (15 peaks): δ = 41.1, 70.9, 77.2, 117.0, 127.0, 127.5, 127.6, 127.7, 128.3, 128.4, 129.3, 132.9, 134.4, 138.2, 139.4. HRMS: m/e calcd for C₁₇H₁₇ClO: 272.0968 [M]; found: 271.0894 [M - 1].

19i

Compound 1i (Method A, 43%): ¹H NMR: δ = 1.18 (t, 3 H, J = 7.18 Hz), 1.84 (s, 3 H), 2.26-2.42 (m, 2 H), 3.32-3.42 (m, 2 H), 4.78-4.85 (m, 3 H), 7.08-7.52 (m, 4 H). ¹³C (13 peaks): δ = 15.3, 22.9, 45.2, 64.6, 79.1, 112.4, 123.0, 127.6, 127.7, 128.6, 132.6, 142.1, 142.6. HRMS: m/e calcd for C₁₃H₁₇BrO: 268.0463 [M]; found: 267.0379 [M - 1].