A New Variant of Reformatsky-Claisen
Rearrangement Mediated by Indium Chloride

Jun Ishihara; Noriko Koyama; Yukihiro Nishino; Keisuke Takahashi; Susumi Hatakeyama

doi:10.1055/s-0029-1217716

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Synlett 2009(14): 2351-2355
DOI: 10.1055/s-0029-1217716

LETTER

A New Variant of Reformatsky-Claisen Rearrangement Mediated by Indium Chloride

Jun Ishihara*, Noriko Koyama, Yukihiro Nishino, Keisuke Takahashi, Susumi Hatakeyama*
Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852851, Japan
Fax: +81(95)8192426; e-Mail: jishi@nagasaki-u.ac.jp;

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Publication History

Received 22 May 2009
Publication Date:
31 July 2009 (online)

Abstract
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Abstract

A new variant of Reformatsky-Claisen rearrangement is described. The reaction of an allyl α-bromo ester in the presence of indium(I) chloride provides a general entry into the functionalized synthon.

Key words

indium - Claisen rearrangement - Reformatsky reaction - carboxylic acid - α-bromo ester

References and Notes

For examples, see:
1a Ziegler FE. Acc. Chem. Res. 1977, 10: 227

Google Scholar
1b Tadano K.-I. In Studies in Natural Products Chemistry: Stereoselective Synthesis, (Part F) . Elsevier; Amsterdam: 1992. p.405

Google Scholar
1c Ito S. Tsunoda T. Pure Appl. Chem. 1994, 66: 2071

Google Scholar
1d Nubbemeyer U. Top. Curr. Chem. 2005, 244: 149

Google Scholar
2a For reviews, see: The Claisen Rearrangement: Methods and Applications Hiersemann M. Nubbemeyer U. Wiley-VCH; Weinheim: 2007.

Google Scholar
See also:
2b Bennett GB. Synthesis 1977, 589

Google Scholar
2c Blechert S. Synthesis 1989, 71

Google Scholar
2d Wipf P. In Comprehensive Organic Synthesis Vol. 5: Trost BM. Pergamon Press; Oxford: 1991. p.827

Google Scholar
2e Martin Castro AM. Chem. Rev. 2004, 104: 2939

Google Scholar
3 Baldwin JE. Walker JA. J. Chem. Soc., Chem. Commun. 1973, 117

Crossref Google Scholar
4 Ireland RE. Mueller RH. Willard AK. J. Am. Chem. Soc. 1976, 98: 2868

Crossref Google Scholar
5a Ireland RE. Mueller RH. J. Am. Chem. Soc. 1972, 94: 5897

Google Scholar
5b Ireland RE. Wipf P. Armstrong JD. J. Org. Chem. 1991, 56: 650

Google Scholar
5c Ireland RE. Wipf P. Xiang J.-N. J. Org. Chem. 1991, 56: 3572

Google Scholar
5d For a review, see: Pereira S. Srebnik M. Aldrichimica Acta 1993, 26: 17

Google Scholar
6a Wada M. Shigehisa T. Akiba K. Tetrahedron Lett. 1985, 26: 5191

Google Scholar
6b Greuter H. Lang RW. Romann AJ. Tetrahedron Lett. 1988, 29: 3291

Google Scholar
6c Zaman S. Kitamura M. Narasaka K. Bull. Chem. Soc. Jpn. 2003, 76: 1055

Google Scholar
6d Yang Y.-Y. Meng W.-D. Qing F.-L. Org. Lett. 2004, 6: 4257

Google Scholar
6e Yang Y.-Y. Xu J. You Z.-W. Xu X.-H. Qiu X.-L. Qing F.-L. Org. Lett. 2007, 9: 5437

Google Scholar
6f Zheng F. Zhang X. Qing F.-L. Chem. Commun. 2009, 1505

Google Scholar
7 Chao L.-C. Rieke RD. J. Org. Chem. 1975, 40: 2253

Crossref Google Scholar
8a Babu SA. Yasuda M. Shibata I. Baba A. Org. Lett. 2004, 6: 4475

Google Scholar
8b Babu SA. Yasuda M. Shibata I. Baba A. J. Org. Chem. 2005, 70: 10408

Google Scholar
8c Babu SA. Yasuda M. Okabe Y. Shibata I. Baba A. Org. Lett. 2006, 8: 3029

Google Scholar

9

General Procedure: A mixture of TMSCl (0.7 mL, 5.5 mmol) and Et₃N (0.7 mL, 5.0 mmol) was centrifuged at 3000 rpm for 5 min. The supernatant (0.64 mL, containing 2.5 mmol of TMSCl) was added to a mixture of dried InCl₃ (158 mg, 0.72 mmol) and In (82 mg, 0.72 mmol) in MeCN (2 mL). To the stirred mixture was added a solution of 4d (100 mg, 0.36 mmol) in MeCN (3 mL) and the reaction mixture was stirred at 10-30 ˚C for 3 h under ultrasonication. The stirred mixture was diluted with sat. NH₄Cl (4 mL), and the aqueous layer was extracted with EtOAc (2 × 20 mL). Drying over MgSO₄, concentration, and silica gel chromatography (SiO₂: 14 g; hexane-EtOAc, 10:1) afforded 5d (55 mg, 0.31 mmol, 80%) and 6d (5.3 mg, 0.03 mmol, 7%).

10

2: IR (neat): 3400(br), 2940, 2859, 1702, 1448, 1255, 1051, 925, 844, 761 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 5.70-5.81 (m, 1 H), 5.08 (d, J = 16.8 Hz, 1 H), 5.04 (d, J = 11.6 Hz, 1 H), 2.28 (d, J = 7.6 Hz, 2 H), 1.62-1.58 (m, 4 H), 1.35-1.46 (m, 2 H), 1.26-1.30 (m, 4 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 182.6, 133.3, 117.7, 47.1, 44.3, 33.4, 25.3, 22.9. MS (EI): m/z = 123, 168 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₀H₁₆O₂: 168.1151; found: 168.1126.
5d: IR (neat): 3200(br), 2981, 1744, 1700, 1467, 1367, 1243, 1162, 1039, 929, 686, 606 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 5.64 (dt, J = 16.8, 10.4 Hz, 1 H), 5.21 (dd, J = 10.4, 1.6 Hz, 1 H), 5.19 (dd, J = 16.8, 0.6 Hz, 1 H), 4.03-4.20 (m, 2 H), 2.77-2.82 (m, 1 H), 2.00 (s, 3 H), 1.17 (s, 6 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 183.4, 170.8, 134.0, 119.7, 63.9, 49.7, 43.2, 24.4, 20.2. MS (EI): m/z = 200 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₀H₁₆O₄: 200.1048; found: 200.1027.
8a: IR (neat): 2979, 1708, 1455, 1364, 1272, 1104, 923, 848, 737, 698, 605 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 7.21-7.35 (m, 5 H), 5.67 (dt, J = 17.8, 9.3 Hz, 1 H), 5.15-5.21 (m, 2 H), 4.47 (s, 2 H), 3.47 (dd, J = 15.9, 8.8 Hz, 2 H), 2.79 (dd, J = 15.9, 6.6 Hz, 1 H), 1.16 (s, 3 H), 1.13 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 183.7, 138.2, 135.3, 128.3, 128.3, 127.5, 119.1, 72.9, 70.5, 50.7, 43.5, 24.8, 20.4. MS (EI): m/z = 248 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₅H₂₀O₃: 248.1413; found: 248.1397. 8b: IR (neat): 2930, 1703, 1470, 1389, 1256, 1103, 1004, 921, 837, 776, 666 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 5.69 (ddd, J = 16.8, 10.2, 9.9 Hz, 1 H), 5.17 (dd, J = 10.2, 1.9 Hz, 1 H), 5.15 (dd, J = 16.7, 1.9 Hz, 1 H), 3.68 (t, J = 5.4 Hz, 2 H), 2.56 (dt, J = 9.3, 6.0 Hz, 1 H), 1.19 (d, J = 7.1 Hz, 6 H), 0.88 (s, 9 H), 0.05 (s, 6 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 183.9, 135.4, 119.0, 63.7, 52.8, 43.2, 25.9, 20.4, 18.3, -5.6. MS (EI): m/z = 273 [M + H⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₄H₂₈O₃Si: 272.1808; found: 272.1785. 8c: IR (neat): 2943, 1704, 1469, 1354, 1265, 1122, 1034, 908, 815, 685, 545 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 5.59-5.75 (m, 1 H), 5.17 (dd, J = 17.6, 1.7 Hz, 1 H), 5.16 (dd, J = 11.3, 2.2 Hz, 1 H), 4.59 (s, 2 H), 3.69-3.90 (m, 2 H), 3.29-3.55 (m, 2 H), 2.79 (dt, J = 6.9, 2.2 Hz, 1 H), 1.42-1.89 (m, 6 H), 1.17 (s, 3 H), 1.13 (s, 3 H). MS (EI): m/z = 243
[M + H⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₃H₂₂O₄: 242.1518; found: 242.1518. 10a: IR (neat): 2980, 1698, 1470, 1413, 1281, 1184, 926, 742, 706, 513 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 7.20-7.31 (m, 5 H), 6.25 (dt, J = 17.6, 9.6 Hz, 1 H), 5.15 (dd, J = 10.9, 0.6 Hz, 1 H), 5.14 (dd, J = 17.5, 0.6 Hz, 1 H), 3.63 (d, J = 9.6 Hz, 1 H), 1.18 (s, 3 H), 1.13 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 183.9, 140.0, 136.6, 129.3, 128.0, 126.8, 117.8, 57.3, 46.7, 23.2, 21.8. MS (EI): m/z = 204 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₃H₁₆O₂: 204.1150; found: 204.1146.
10b: IR (neat): 2979, 1702, 1611, 1513, 1469, 1250, 1180, 1037, 922, 832, 540 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 7.13 (d, J = 8.8 Hz, 2 H), 6.83 (d, J = 8.8 Hz, 2 H), 6.21 (dt, J = 17.6, 10.1 Hz, 1 H), 5.13 (d, J = 11.0 Hz, 1 H), 5.12 (dd, J = 15.9, 0.9 Hz, 1 H), 3.71 (s, 3 H), 3.59 (d, J = 9.6 Hz, 1 H), 1.17 (s, 3 H), 1.12 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 183.7, 158.4, 136.9, 132.0, 130.2, 117.5, 113.4, 56.5, 55.1, 46.8, 23.1, 21.8. MS (EI): m/z = 234 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₄H₁₈O₃: 234.1255; found: 234.1237.
10c: IR (neat): 2980, 1707, 1489, 1404, 1276, 1076, 1011, 925, 828, 516 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 7.42 (d, J = 8.5 Hz, 2 H), 7.09 (d, J = 8.5 Hz, 2 H), 6.18 (dt, J = 16.8, 9.9 Hz, 1 H), 5.17 (dd, J = 11.2, 0.9 Hz, 1 H), 5.14 (dd, J = 16.7, 0.8 Hz, 1 H), 3.60 (d, J = 9.3 Hz, 1 H), 1.18 (s, 3 H), 1.12 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 183.6, 139.0, 136.0, 131.2, 130.9, 120.8, 118.3, 56.6, 46.6, 22.9, 22.0. MS (EI): m/z = 282 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₃H₁₅ ⁷⁹BrO₂: 282.0255; found: 282.0270.
10e: IR (neat): 2981, 1706, 1471, 1274, 1167, 1030, 925, 874, 793, 602 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 7.35 (s, 1 H), 7.26 (s, 1 H), 6.30 (s, 1 H), 6.00 (dt, J = 17.6, 9.3 Hz, 1 H), 5.15 (d, J = 11.8 Hz, 1 H), 5.14 (d, J = 15.1 Hz,
1 H), 3.61 (d, J = 9.1 Hz, 1 H), 1.19 (s, 3 H), 1.14 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 183.7, 142.5, 140.1, 136.1, 123.5, 117.8, 110.8, 48.0, 29.7, 22.6, 22.2. MS (EI): m/z = 194 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₁H₁₄O₃: 194.0943; found: 194.0939.
12: IR (neat): 2974, 1709, 1473, 1409, 1383, 1241, 1201, 1162, 943, 557 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 5.12 (tt, J = 7.7, 1.4 Hz, 1 H), 2.26 (d, J = 7.7 Hz, 2 H), 1.72 (s, 3 H), 1.61 (s, 3 H), 1.19 (s, 6 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 184.7, 134.6, 119.6, 42.7, 38.4, 26.0, 24.5, 17.9. MS (EI): m/z = 156 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₉H₁₆O₂: 156.1151; found: 156.1131.
14: IR (neat): 2984, 1742, 1700, 1471, 1417, 1385, 1242, 1037, 921, 606, 452, 440 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 5.90 (dd, J = 17.4, 10.9 Hz, 1 H), 5.20 (dd, J = 10.9, 0.8 Hz, 1 H), 5.08 (dd, J = 17.3, 0.8 Hz, 1 H), 4.26 (d, J = 11.1 Hz, 1 H), 4.13 (d, J = 11.1 Hz, 1 H), 2.02 (s, 3 H), 1.20 (s, 3 H), 1.19 (s, 3 H), 1.16 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 182.8, 171.0, 139.5, 115.7, 68.1, 46.8, 44.4, 21.6, 20.8, 16.7. MS (EI): m/z = 214 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₁H₁₈O₄: 214.1205; found: 214.1197.
16: IR (neat): 2978, 1700, 1468, 1375, 1293, 1131, 1009, 915, 740, 553 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 5.98 (dd, J = 17.3, 11.0 Hz, 1 H), 5.04 (dd, J = 10.7, 1.1 Hz, 1 H), 5.00 (dd, J = 17.3, 1.4 Hz, 1 H), 1.16 (s, 6 H), 1.10 (s, 6 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 183.9, 144.4, 112.5, 47.8, 40.9, 22.9, 21.4. MS (EI): m/z = 156 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₉H₁₆O₂: 156.1150; found: 156.1142.
18: IR (neat): 2979, 1955, 1705, 1455, 1360, 1284, 1069, 851, 739, 699 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 7.23-7.38 (m, 5 H), 4.94 (t, J = 2.1 Hz, 2 H), 4.59 (s, 2 H), 4.13 (t, J = 1.9 Hz, 2 H), 1.38 (s, 6 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 207.4, 182.0, 137.9, 128.3, 127.7, 127.5, 104.5, 78.1, 71.9, 68.8, 43.0, 24.9. MS (EI): m/z = 246 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₅H₁₈O₃: 246.1255; found: 246.1257.
20: IR (neat): 2929, 1702, 1469, 1367, 1279, 1149, 942, 859, 721, 619 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 5.79 (dd,
J = 10.3, 3.2 Hz, 1 H), 5.53 (d, J = 9.9 Hz, 1 H), 2.46-2.60 (m, 1 H), 1.40-2.20 (m, 6 H), 1.26 (s, 6 H). MS (EI): m/z = 168 [M⁺]. HRMS (EI): m/z [M⁺] calcd for C₁₀H₁₆O₂: 168.1150; found: 168.1168.
22: IR (neat): 2928, 1732, 1469, 1370, 1225, 1131, 1080, 1043, 794, 642, 605 cm^-¹. ^¹H NMR (300 MHz, CDCl₃):
δ = 5.85 (s, 2 H), 5.26 (dd, J = 9.2, 2.9 Hz, 1 H), 4.42 (d, J = 2.3 Hz, 1 H), 4.25 (dd, J = 11.8, 2.7 Hz, 1 H), 4.17 (dd, J = 11.8, 5.5 Hz, 1 H), 3.74 (dt, J = 2.7, 3.1 Hz, 1 H), 2.09 (s, 3 H), 2.07 (s, 3 H), 1.21 (s, 3 H), 1.18 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 180.5, 171.2, 170.6, 128.6, 127.6, 78.7, 74.1, 65.4, 63.2, 46.3, 21.0, 21.7, 20.5. MS (EI): m/z = 300 [M⁺].