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

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

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;

Further Information

Publication History

Received 5 October 2006
Publication Date:
20 December 2006 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

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

1a Handbook of Organopalladium Chemistry for Organic Synthesis Vol. II: Negishi E. Wiley; New York: 2002. p.2309

Crossref Google Scholar
For recent reviews, see:
1b Nakamura I. Yamamoto Y. Chem. Rev. 2004, 104: 2127

Crossref Google Scholar
1c Zeni G. Larock RC. Chem. Rev. 2004, 104: 2285

Crossref Google Scholar
1d Alonso F. Beletskaya IP. Yus M. Chem. Rev. 2004, 104: 3079

Crossref Google Scholar
1e Tietze LF. Ila H. Bell HP. Chem. Rev. 2004, 104: 3453

Crossref Google Scholar
1f Soderberg BCG. Coord. Chem. Rev. 2004, 248: 1085

Crossref Google Scholar
1g Vizer SA. Yerzhanov KB. Quntar AAAA. Dembitsky VM. Tetrahedron 2004, 60: 5499

Crossref Google Scholar
1h Muzart J. Tetrahedron 2005, 61: 5955

Crossref Google Scholar
1i Asao N. Synlett 2006, 1645

Crossref Google Scholar
1j Miki K. Uemura S. Ohe K. Chem. Lett. 2005, 34: 1068

Crossref Google Scholar
Hydration of alkynes:
2a Fukuda Y. Utimoto K. J. Org. Chem. 1991, 56: 3729

Crossref Google Scholar
2b Casado R. Contel M. Laguna M. Romero P. Sanz S. J. Am. Chem. Soc. 2003, 125: 11925

Crossref Google Scholar
2c Mizushima E. Sato K. Hayashi T. Tanaka M. Angew. Chem. Int. Ed. 2002, 41: 4563

Crossref Google Scholar
2d Teles JH. Brode S. Chabanas M. Angew. Chem. Int. Ed. 1998, 37: 1415

Crossref Google Scholar
For recent examples of intramolecular cyclizations, see:
2e Liu Y. Song F. Guo S. J. Am. Chem. Soc. 2006, 128: 11332

Crossref Google Scholar
2f Genin E. Toullec PY. Antoniotti S. Brancour C. Genet J.-P. Michelet V. J. Am. Chem. Soc. 2006, 128: 3112

Crossref Google Scholar
2g Kang J.-E. Kim H.-B. Lee J.-W. Shin S. Org. Lett. 2006, 8: 3537

Crossref Google Scholar
2h Liu Y. Liu M. Guo S. Tu H. Zhou Y. Gao H. Org. Lett. 2006, 8: 3445

Crossref Google Scholar
2i Buzas A. Gagosz F. Org. Lett. 2006, 8: 515

Crossref Google Scholar
2j Asao N. Sato K. Yamamoto Y. Tetrahedron Lett. 2003, 44: 5675

Crossref Google Scholar
1,2-Migration of acyl group:
3a Mamane V. Gress T. Krause H. Fürstner A. J. Am. Chem. Soc. 2004, 126: 8654

Crossref Google Scholar
3b Shi X. Gorin DJ. Toste FD. J. Am. Chem. Soc. 2005, 127: 5802

Crossref Google Scholar
3c Prasad BAB. Yoshimoto FK. Sarpong R. J. Am. Chem. Soc. 2005, 127: 12468

Crossref Google Scholar
3d Johansson MJ. Gorin DJ. Staben ST. Toste FD. J. Am. Chem. Soc. 2005, 127: 18002

Crossref Google Scholar
3e Pujanauski BG. Prasad BAB. Sarpong R. J. Am. Chem. Soc. 2006, 128: 6786

Crossref Google Scholar
For 1,3-migration of acyl group, see:
3f Cariou K. Mainetti E. Fensterbank L. Malacria M. Tetrahedron 2004, 60: 9745

Crossref Google Scholar
3g Zhang L. J. Am. Chem. Soc. 2005, 127: 16804

Crossref Google Scholar
3h Marion N. Diez-Gonzalez S. Fremont P. Noble AR. Nolan SP. Angew. Chem. Int. Ed. 2006, 45: 3647

Crossref Google Scholar
3i Zhang L. Wang S. J. Am. Chem. Soc. 2006, 128: 1442

Crossref Google Scholar
3j Zhao J. Hughes CO. Toste FD. J. Am. Chem. Soc. 2006, 128: 7436

Crossref Google Scholar
3k Wang S. Zhang L. J. Am. Chem. Soc. 2006, 128: 8414

Crossref Google Scholar
4 Maurer H. Hopf H. Eur. J. Org. Chem. 2005, 2702

Crossref Google Scholar
5a Kato K. Nishimura A. Yamamoto Y. Akita H. Tetrahedron Lett. 2001, 42: 4203

Crossref Google Scholar
5b Takayama H. Kato K. Akita H. Eur. J. Org. Chem. 2006, 644

Crossref Google Scholar
5c Kato K. Matsuba C. Kusakabe T. Takayama H. Yamamura S. Mochida T. Akita H. Peganova TA. Vologdin NV. Gusev OV. Tetrahedron 2006, 62: 9988

Crossref Google Scholar
5d Kato K. Yamamoto Y. Akita H. Tetrahedron Lett. 2002, 43: 4915

Crossref Google Scholar
5e Kato K. Yamamoto Y. Akita H. Tetrahedron Lett. 2002, 43: 6587

Crossref Google Scholar
5f Kato K. Nouchi H. Ishikura K. Takaishi S. Motodate S. Tanaka H. Okudaira K. Mochida T. Nishigaki R. Shigenobu K. Akita H. Tetrahedron 2006, 62: 2545

Crossref Google Scholar

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.