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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References

References and Notes

<A NAME="RS01306ST-1A">1a</A> Giese B. In Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds Pergamon Press; Oxford: 1986.

<A NAME="RS01306ST-1B">1b</A> Stork G. In Radical-Mediated Cyclization Processes - A Goal for Synthetic Efficiency Bartmann W. Trost BM. Verlag Chemie; Basel: 1984.

<A NAME="RS01306ST-2A">2a</A> Majumdar KC. Basu PK. Mukhopadhyay PP. Tetrahedron 2004, 60: 6239

<A NAME="RS01306ST-2B">2b</A> Davies AG. Organotin Chemistry 2nd ed.: Wiley and Sons; London: 2004.

<A NAME="RS01306ST-3">3</A> Duñach E. Franco D. Olivero S. Eur. J. Org. Chem. 2003, 1605

<A NAME="RS01306ST-4">4</A> Olivero S. Rolland J.-P. Duñach E. Organometallics 1998, 17: 3747

<A NAME="RS01306ST-5A">5a</A> Hong B.-C. Sarshar S. Org. Prep. Proced. Int. 1999, 1: 1

<A NAME="RS01306ST-5B">5b</A> Wickens P, Cantin L.-D, Chuang C.-Y, Dai M, Hentemann MF, Kumarasinghe E, Liang SX, Lowe DB, Shelekhin TE, Wang Y, Zhang C, Zhang H.-J, and Zhao Q. inventors; PCT Int. Appl., WO 2004011446.

<A NAME="RS01306ST-5C">5c</A> Sekiguchi T, Nakagawa S, and Fujikura Y. inventors; JP 03044337.

<A NAME="RS01306ST-5D">5d</A> Meakins SE, and Motion KR. inventors; Eur. Pat. Appl., EP 393742.

<A NAME="RS01306ST-5E">5e</A> Frank WC. inventors; USA, US 93-79008.

<A NAME="RS01306ST-5F">5f</A> Ohnuma H, Fujikura Y, Fujita M, and Toi N. inventors; Eur. Pat. Appl., EP 385497.

<A NAME="RS01306ST-5G">5g</A> Sprecker MA, Weiss RA, Belko RP, and Molner EA. inventors; USA, US 6342612.

<A NAME="RS01306ST-6A">6a</A> Wickens P, Cantin L.-D, Chuang C.-Y, Dai M, Hentemann MF, Kumarasinghe E, Liang SX, Lowe DB, Shelekhin TE, Wang Y, Zhang C, Zhang H.-J, and Zhao Q. inventors; PCT Int. Appl., WO 2004011446.

<A NAME="RS01306ST-6B">6b</A> Sekiguchi T, Nakagawa S, and Fujikura Y. inventors; JP 03044337.

<A NAME="RS01306ST-6C">6c</A> Meakins SE, and Motion KR. inventors; Eur. Pat. Appl., EP 393742.

<A NAME="RS01306ST-6D">6d</A> Frank WC. inventors; USA, US 93-79008.

<A NAME="RS01306ST-7">7</A> Anzalone PW. Baru AR. Danielson EM. Hayes PD. Nguyen MP. Panico AF. Smith RC. Mohan RS. J. Org. Chem. 2005, 70: 2091

<A NAME="RS01306ST-8A">8a</A> Reglinski J. In Chemistry of Arsenic, Antimony and Bismuth Norman NC. Blackie Academic and Professional; New York: 1998. p.403-440

<A NAME="RS01306ST-8B">8b</A> Organobismuth Chemistry Suzuki H. Matano Y. Elsevier; Amsterdam: 2001.

<A NAME="RS01306ST-8C">8c</A> Leonard NM. Wieland LC. Mohan RS. Tetrahedron 2002, 58: 8373

<A NAME="RS01306ST-8D">8d</A> Antoniotti S. Synlett 2003, 1566

<A NAME="RS01306ST-8E">8e</A> Gaspard-Iloughmane H. Le Roux C. Eur. J. Org. Chem. 2004, 2517

<A NAME="RS01306ST-9">9</A> Bosnich B. Tobe ML. Webb GA. Inorg. Chem. 1965, 4: 1109

<A NAME="RS01306ST-10">10</A> Gosden C. Healy KP. Pletcher D. J. Chem. Soc., Dalton Trans. 1978, 8: 972

<A NAME="RS01306ST-11">11</A> Duñach E. Esteves AP. Medeiros MJ. Olivero S. New J. Chem. 2005, 4: 633

<A NAME="RS01306ST-12">12</A> Armstrong DW. Gahm KH. Chang LW. Microchem. J. 1997, 57: 149

<A NAME="RS01306ST-13">13</A> Izumi T. Murakami S. J. Chem. Technol. Biotechnol. 1994, 60: 23

<A NAME="RS01306ST-14">14</A> Miura M. Yoshida M. Nojima M. Kusabayashi S. J. Chem. Soc., Perkin Trans. 1 1982, 1: 79

<A NAME="RS01306ST-15">15</A> Yadav JS. Subba Reddy VB. Srihari P. Synlett 2001, 673

<A NAME="RS01306ST-16">16</A> Watahiki T. Akabane Y. Mori S. Oriyama T. Org. Lett. 2003, 5: 3045

<A NAME="RS01306ST-17">17</A> Hosomi A. Masahiko E. Sakurai H. Chem. Lett. 1976, 941

<A NAME="RS01306ST-18">18</A> Aggarwal VK. Vennall GP. Synthesis 1998, 1822

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].

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].

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].

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].

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].

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.

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.

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].

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].