A Gold(III)-Catalyzed Double Wacker-Type Reaction of 1,1-Diethynyl Acetate

Keisuke Kato; Ryuhei Teraguchi; Taichi Kusakabe; Satoshi Motodate; Shigeo Yamamura; Tomoyuki Mochida; Hiroyuki Akita

doi:10.1055/s-2006-956497

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Synlett 2007(1): 0063-0066
DOI: 10.1055/s-2006-956497

LETTER

A Gold(III)-Catalyzed Double Wacker-Type Reaction of 1,1-Diethynyl Acetate

Keisuke Kato*^a, Ryuhei Teraguchi^a, Taichi Kusakabe^a, Satoshi Motodate^a, Shigeo Yamamura^a, Tomoyuki Mochida^b, Hiroyuki Akita*^a
^a Faculty of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan
^b Department of Chemistry, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan
Fax: +81(474)721825; e-Mail: kkk@phar.toho-u.ac.jp;

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Publikationsverlauf

Received 5 October 2006
Publikationsdatum:
20. Dezember 2006 (online)

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Abstract

Treatment of 1,1-diethynyl acetates in the presence of Au or Pt catalyst (5 mol%) in methanol at 60 °C for 20-48 hours gave γ-ketoesters and lactones in 40-54% and 19-39% yields, respectively. An oxygen atom is introduced to the first acetylene moiety in accordance with Markovnikov’s rule, and to the second acetylene moiety with anti-Markovnikov regioselectivity.

Key words

1,1-diethynyl acetates - double Wacker-type reaction - gold - platinum - catalyst

References and Notes

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6

Preparation of Substrates 2; General Procedure: To a solution of trimethylsilyl acetylene (3.32 g, 33.8 mmol) in THF (30 mL) under Ar was added n-BuLi (13.0 mL of 2.6 M in hexane, 33.8 mmol) at -78 °C and the mixture was stirred for 0.5 h at 0 °C. After the solution was cooled to -78 °C, the corresponding ester 1 (11.3 mmol) in THF (3 × 8 mL) was slowly added dropwise. The mixture was stirred at -10 °C for 12 h and quenched with H₂O (80 mL) and EtOAc (80 mL). The organic layers were separated, the aqueous layer was extracted with EtOAc (50 mL), and combined organic layers were dried with MgSO₄ and concentrated in vacuo. To a solution of the crude product in THF (30 mL) was added TBAF (22.4 mL of 1 M in THF, 22.4 mmol) and the mixture was stirred for 0.5 h at r.t. The mixture was diluted with H₂O (80 mL) and EtOAc (80 mL). The organic layers were separated, the aqueous layer was extracted with EtOAc (2 × 50 mL), and combined organic layers were dried with MgSO₄ and concentrated in vacuo. To a solution of the crude product in pyridine (3 mL) and Ac₂O (2 mL) was added 4-dimethylaminopyridine (50 mg) and the mixture was stirred for 3-10 h at r.t. The mixture was diluted with H₂O (50 mL) and EtOAc (50 mL). The organic layers were separated, the aqueous layer was extracted with EtOAc (50 mL), and combined organic layers were washed with aq 10% HCl, dried with MgSO₄ and concentrated in vacuo. The crude product was purified by column chromatography on silica gel. The fraction eluted with hexane-EtOAc (100:1-20:1) afforded 2. 2a: colorless needles; mp 51 °C. ¹H NMR (CDCl₃): δ = 2.09 (s, 3 H), 2.37-2.41 (m, 2 H), 2.70 (s, 2 H), 2.93-2.97 (m, 2 H), 7.19-7.32 (m, 5 H). ¹³C NMR (CDCl₃): δ = 21.3, 30.4, 43.8, 66.3, 74.4, 80.0, 126.2, 128.5, 128.5, 140.6, 168.3. FAB-MS: m/z = 249 [M⁺ + Na]. IR (KBr): 3253, 2935, 2120, 1748 cm^-1. Anal. Calcd for C₁₅H₁₄O₂: C, 79.62; H, 6.24. Found: C, 79.41; H, 6.41. 2b: colorless oil. ¹H NMR (CDCl₃): δ = 2.07 (s, 3 H), 2.66 (s, 2 H), 3.37 (s, 2 H), 7.25-7.39 (m, 5 H). ¹³C NMR (CDCl₃): δ = 21.4, 47.6, 66.7, 74.9, 79.8, 127.5, 127.9, 131.2, 133.7, 168.2. HRMS-EI: m/z [M⁺] calcd for C₁₄H₁₂O₂: 212.0837; found: 212.0833. IR (KBr): 3270, 2122, 1744 cm^-1. 2c: colorless oil. ¹H NMR (CDCl₃): δ = 0.89 (t, J = 6.8 Hz, 3 H), 1.26-1.38 (m, 10 H), 1.58-1.66 (m, 2 H), 2.04-2.08 (m, 2 H), 2.09 (s, 3 H), 2.64 (s, 2 H). ¹³C NMR (CDCl₃): δ = 14.1, 21.4, 22.7, 23.9, 29.1, 29.2, 29.4, 31.8, 42.2, 66.8, 73.5, 80.3, 168.3. FAB-MS: m/z = 235 [M⁺ + H]. IR (KBr): 3291, 2929, 2123, 1757 cm^-1. Anal. Calcd for C₁₅H₂₂O₂: C, 77.88; H, 9.46. Found: C, 76.12; H, 9.53. 2d: colorless oil. ¹H NMR (CDCl₃): δ = 0.92 (t, J = 7.0 Hz, 3 H), 1.33-1.38 (m, 4 H), 1.59-1.67 (m, 2 H), 2.03-2.08 (m, 2 H), 2.09 (s, 3 H), 2.64 (s, 2 H). ¹³C NMR (CDCl₃): δ = 13.9, 21.4, 22.4, 23.6, 31.3, 42.2, 66.8, 73.6, 80.3, 168.4. HRMS-EI: m/z [M⁺] calcd for C₁₂H₁₆O₂: 192.1150; found: 192.1143. IR (KBr): 3292, 2958, 2123, 1756 cm^-1. 2e: colorless needles; mp 47 °C. ¹H NMR (CDCl₃): δ = 2.09 (s, 3 H), 2.69 (s, 2 H), 4.36 (s, 2 H), 6.97-7.01 (m, 3 H), 7.24-7.31 (m, 2 H). ¹³C NMR (CDCl₃): δ = 21.2, 65.7, 73.4, 74.9, 77.7, 115.4, 121.9, 129.5, 158.4, 168.1. HRMS-EI: m/z [M⁺] calcd for C₁₄H₁₂O₃: 228.0787; found: 228.0786. IR (KBr): 3281, 2132, 1767 cm^-1.

7

Reaction of 2; General Procedure: A 20-mL round-bottomed flask, containing a magnetic stirring bar, catalyst (0.015 mmol), 2 (0.3 mmol) and MeOH (5 mL) was fitted with a Dimroth condenser capped with a rubber septum. After being stirred for a certain period at 60 °C, the mixture was diluted with EtOAc (20 mL) and washed with aq 3% NaHCO₃ (20 mL). The organic layers were separated, the aqueous layer was extracted with EtOAc (30 mL), and combined organic layers were dried with MgSO₄ and concentrated in vacuo. The crude product was purified by column chromatography on silica gel. The fraction eluted with hexane-EtOAc (100:1-50:1 and 10:1) afforded 3 and 4, respectively. 3a: colorless oil. ¹H NMR (CDCl₃): δ = 1.69-1.78 (m, 1 H), 1.91-2.00 (m, 1 H), 2.22 (s, 3 H), 2.43 (dd, J = 4.4, 16.8 Hz, 1 H), 2.58-2.62 (m, 2 H), 2.80 (dd, J = 9.6, 16.8 Hz, 1 H), 2.99-3.07 (m, 1 H), 3.66 (s, 3 H), 7.15-7.32 (m, 5 H). ¹³C NMR (CDCl₃): δ = 29.5, 32.8, 33.1, 34.9, 47.4, 51.7, 126.2, 128.2, 128.5, 140.9, 172.7, 210.5. HRMS-EI: m/z [M⁺] calcd for C₁₄H₁₈O₃: 234.1256; found: 234.1252. IR (KBr): 1736, 1712 cm^-1. 3b: colorless oil. ¹H NMR (CDCl₃): δ = 2.06 (s, 3 H), 2.28 (dd, J = 4.4, 17.0 Hz, 1 H), 2.54 (dd, J = 8.4, 13.6 Hz, 1 H), 2.70 (dd, J = 10.0, 17.0 Hz, 1 H), 2.87 (dd, J = 7.2, 13.6 Hz, 1 H), 3.18-3.25 (m, 1 H), 3.55 (s, 3 H), 7.07-7.24 (m, 5 H). ¹³C NMR (CDCl₃): δ = 30.3, 35.0, 37.6, 49.6, 51.6, 126.7, 128.6, 128.8, 138.1, 172.6, 210.6. HRMS-EI: m/z [M⁺] calcd for C₁₃H₁₆O₃: 220.1100; found: 220.1097. IR (KBr): 1738, 1205 cm^-1. 3c: colorless oil. ¹H NMR (CDCl₃): δ = 0.81 (t, J = 6.8 Hz, 3 H), 1.14-1.38 (m, 13 H), 1.49-1.56 (m, 1 H), 2.16 (s, 3 H), 2.28 (dd, J = 4.4, 16.8 Hz, 1 H), 2.67 (dd, J = 10.0, 16.8 Hz, 1 H), 2.88-2.95 (m, 1 H), 3.58 (s, 3 H). ¹³C NMR (CDCl₃): δ = 14.0, 22.6, 26.8, 29.1, 29.3, 29.5, 29.5, 31.3, 31.8, 34.9, 47.9, 51.6, 173.0, 210.9. HRMS-EI: m/z [M⁺] calcd for C₁₄H₂₆O₃: 242.1882; found: 242.1893. IR (KBr): 2928, 1739, 1715 cm^-1. 3d: colorless oil. ¹H NMR (CDCl₃): δ = 0.81 (t, J = 6.8 Hz, 3 H), 1.17-1.21 (m, 6 H), 1.25-1.38 (m, 1 H), 1.50-1.59 (m, 1 H), 2.16 (s, 3 H), 2.28 (dd, J = 4.4, 16.8 Hz, 1 H), 2.67 (dd, J = 10.0, 16.8 Hz, 1 H), 2.88-2.95 (m, 1 H), 3.58 (s, 3 H). ¹³C NMR (CDCl₃): δ = 13.9, 22.3, 26.5, 29.5, 31.2, 31.7, 34.9, 47.9, 51.6, 172.9, 210.9. HRMS-EI: m/z [M⁺] calcd for C₁₁H₂₀O₃: 200.1413; found: 200.1416. IR (KBr): 2932, 1739, 1714 cm^-1. 3f: colorless oil. ¹H NMR (CDCl₃): δ = 0.92 (d, J = 6.8 Hz, 6 H), 1.69-1.78 (m, 1 H,), 1.86-2.01 (m, 2 H), 2.22 (s, 3 H), 2.44 (dd, J = 4.8, 16.8 Hz, 1 H), 2.55-2.66 (m, 2 H), 2.81 (dd, J = 9.6, 16.8 Hz, 1 H), 2.99-3.06 (m, 1 H), 3.80-3.88 (m, 2 H), 7.15-7.31 (m, 5 H). ¹³C NMR (CDCl₃): δ = 19.0, 27.6, 29.5, 32.9, 33.1, 35.2, 47.5, 70.8, 126.2, 128.2, 128.5, 141.0, 172.3, 210.5. HRMS-EI: m/z [M⁺] calcd for C₁₇H₂₄O₃: 276.1726; found: 276.1721. IR (KBr): 2962, 1733, 1160 cm^-1. 4a: colorless oil. ¹H NMR (CDCl₃): δ = 1.41 (d, J = 6.8 Hz, 3 H), 2.54-2.76 (m, 2 H), 2.92 (t, J = 8.0 Hz, 2 H), 4.90 (dq, J = 1.6, 6.8 Hz, 1 H), 5.81 (q, J = 1.6 Hz, 1 H), 7.18-7.34 (m, 5 H). ¹³C NMR (CDCl₃): δ = 18.2, 29.5, 33.1, 80.4, 115.6, 126.7, 128.1, 128.7, 139.7, 172.9, 173.1. HRMS-EI: m/z [M⁺] calcd for C₁₃H₁₄O₂: 202.0994; found: 202.0996. IR (KBr): 2928, 1755, 1639 cm^-1. 4b: colorless oil. ¹H NMR (CDCl₃): δ = 1.38 (d, J = 6.8 Hz, 3 H), 3.48 (dd, J = 1.6, 16.8 Hz, 1 H), 3.68 (d, J = 16.8 Hz, 1 H), 4.86 (br q, J = 6.8 Hz, 1 H), 5.59 (d, J = 1.6 Hz, 1 H), 7.10-7.30 (m, 5 H). ¹³C NMR (CDCl₃): δ = 18.3, 34.6, 79.9, 116.7, 127.3, 128.8, 129.0, 135.5, 172.6, 172.9. HRMS-EI: m/z [M⁺] calcd for C₁₂H₁₂O₂: 188.0837; found: 188.0834. IR (KBr): 2932, 1737, 1639 cm^-1. 4c: colorless oil. ¹H NMR (CDCl₃): δ = 0.84 (t, J = 6.4 Hz, 3 H), 1.17-1.34 (m, 10 H), 1.38 (d, J = 6.8 Hz, 3 H), 1.48-1.58 (m, 2 H), 2.16-2.37 (m, 2 H), 4.89 (dq, J = 1.6, 6.8 Hz, 1 H), 5.72 (d, J = 1.6 Hz, 1 H). ¹³C NMR (CDCl₃): δ = 14.0, 18.2, 22.5, 26.9, 27.9, 29.0, 29.1, 29.1, 31.7, 80.3, 114.8, 173.1, 174.5. HRMS-EI: m/z [M⁺] calcd for C₁₃H₂₂O₂: 210.1620; found: 210.1629. IR (KBr): 2927, 1755, 1639 cm^-1. 4d: colorless oil. ¹H NMR (CDCl₃): δ = 0.84 (t, J = 7.2 Hz, 3 H), 1.26-1.31 (m, 4 H), 1.36 (d, J = 6.8 Hz, 3 H), 1.49-1.57 (m, 2 H), 2.14-2.35 (m, 2 H), 4.87 (dq, J = 1.2, 6.8 Hz, 1 H), 5.70 (d, J = 1.6 Hz, 1 H). ¹³C NMR (CDCl₃): δ = 13.8, 18.2, 22.2, 26.5, 27.8, 31.3, 80.3, 114.8, 173.1, 174.5. HRMS-EI: m/z [M⁺] calcd for C₁₀H₁₆O₂: 168.1150; found: 168.1144. IR (KBr): 2932, 1754, 1638 cm^-1. 5: colorless oil; diastereomeric mixture, ratio = 2.3:1. ¹H NMR (CDCl₃, major diastereomer): δ = 1.66 (s, 3 H), 2.05-2.25 (m, 2 H), 2.66 (s, 1 H), 2.79-2.96 (m, 2 H), 3.40 (s, 3 H), 4.18 (d, J = 2.8 Hz, 1 H), 4.50 (d, J = 2.8 Hz, 1 H), 7.18-7.32 (m, 5 H). ¹³C NMR (CDCl₃, major diastereomer): δ = 24.0, 30.3, 44.4, 50.1, 73.9, 78.8, 80.8, 82.4, 123.1, 126.1, 128.4, 128.5, 141.0, 159.8. HRMS-EI: m/z [M⁺] calcd for C₁₆H₁₈O₃: 258.1256; found: 258.1258. IR (KBr): 3287, 2117, 1687, 1052 cm^-1.