Synthesis 2013; 45(18): 2605-2611
DOI: 10.1055/s-0033-1338513
paper
© Georg Thieme Verlag Stuttgart · New York

Straightforward and Highly Efficient Synthesis of α-Acetoxy Ketones through Gold-Catalyzed Intermolecular Oxidation of Terminal Alkynes

Chao Wu
a   State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China   Fax: +86(731)88821742   Email: wmhe@hnu.edu.cn   Email: jnxiang@hnu.edu.cn
,
Zhiwu Liang
a   State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China   Fax: +86(731)88821742   Email: wmhe@hnu.edu.cn   Email: jnxiang@hnu.edu.cn
,
Dong Yan
b   Hunan Chemical Industry Vocation Technology Institute, Zhuzhou 412004, P. R. of China
,
Weimin He*
a   State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China   Fax: +86(731)88821742   Email: wmhe@hnu.edu.cn   Email: jnxiang@hnu.edu.cn
,
Jiannan Xiang*
a   State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China   Fax: +86(731)88821742   Email: wmhe@hnu.edu.cn   Email: jnxiang@hnu.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 11.05.2013

Accepted after revision: 03.07.2013

Publication Date:
30 July 2013 (online)


Abstract

A variety of terminal alkynes were efficiently converted into the corresponding α-acetoxy ketones through gold-catalyzed intermolecular oxidation in the presence of 8-methylquinoline 1-oxide as the oxidant. The reaction probably proceeds through an α-oxo gold carbene intermolecular O–H insertion.

Supporting Information

 
  • References

  • 1 Radüchel B. Synthesis 1980; 292

    • For esters as hydroxy functional groups, see:
    • 2a Green TW, Wuts PG. M. Protective Groups in Organic Synthesis . Wiley; New York: 1991
    • 2b Noyori R, Kitamura M In Modern Synthetic Methods . Vol. 5. Scheffold R. Springer; Berlin: 1989: 115
  • 3 Chen Y, Chen C, Wu X. Chem. Soc. Rev. 2012; 41: 1742
    • 4a Paulissen R, Reimlinger H, Hayez E, Hubert AJ, Teyssié P. Tetrahedron Lett. 1973; 14: 2233
    • 4b Shinada T, Kawakami T, Sakai H, Takada I, Ohfune Y. Tetrahedron Lett. 1998; 39: 3757
    • 5a Holshouser MH, Kolb M. J. Pharm. Sci. 1986; 75: 619
    • 5b Rather JB, Reid EE. J. Am. Chem. Soc. 1919; 41: 75
    • 6a Rubottom GM, Grube JM, Kincaid K. Synth. Commun. 1976; 6: 59
    • 6b Demir AS, Camkerten N, Akgun H, Tanyeli C, Mahasneh AS, Watt DS. Synth. Commun. 1990; 20: 2279
    • 6c Lee JC, Jin YS, Choi J.-H. Chem. Commun. 2001; 956
  • 7 Mo D.-L, Dai L.-X, Hou X.-L. Tetrahedron Lett. 2009; 50: 5578
    • 8a Zhang L, Sun J, Kozmin SA. Adv. Synth. Catal. 2006; 348: 2271
    • 8b Hashmi AS. K. Chem. Rev. 2007; 107: 3180
    • 8c Li Z, Brouwer C, He C. Chem. Rev. 2008; 108: 3239
    • 8d Huang H, Zhou Y, Liu H. Beilstein J. Org. Chem. 2011; 7: 897
    • 8e Krause N, Winter C. Chem. Rev. 2011; 111: 1994
    • 8f de Haro T, Nevado C. Synthesis 2011; 2530
    • 8g Adcock HV, Davies PW. Synthesis 2012; 44: 3401
    • 8h Lu B.-L, Dai L, Shi M. Chem. Soc. Rev. 2012; 41: 3318
    • 8i Rudolph M, Hashmi AS. K. Chem. Soc. Rev. 2012; 41: 2448
    • 9a Davies PW, Cremonesi A, Martin N. Chem. Commun. 2011; 47: 379
    • 9b Lu B, Li C, Zhang L. J. Am. Chem. Soc. 2010; 132: 14070
    • 9c Ye L, He W, Zhang L. J. Am. Chem. Soc. 2010; 132: 8550
    • 9d Ye L, Cui L, Zhang G, Zhang L. J. Am. Chem. Soc. 2010; 132: 3258
    • 9e He W, Li C, Zhang L. J. Am. Chem. Soc. 2011; 133: 8482
    • 9f Qian D, Zhang J. Chem. Commun. 2011; 47: 11152
    • 9g Chen D, Song G, Jia A, Li X. J. Org. Chem. 2011; 76: 8488
    • 9h Ye L, He W, Zhang L. Angew. Chem. Int. Ed. 2011; 50: 3236
    • 9i Noey EL, Luo Y, Zhang L, Houk KN. J. Am. Chem. Soc. 2011; 134: 1078
    • 9j Bhunia S, Ghorpade S, Huple DB, Liu R.-S. Angew. Chem. Int. Ed. 2012; 51: 2939
    • 9k Wang Y, Ji K, Lan S, Zhang L. Angew. Chem. Int. Ed. 2012; 51: 1915
    • 9l Dateer RB, Pati K, Liu R.-S. Chem. Commun. 2012; 48: 7200
    • 9m Xie J, Jiang H, Cheng Y, Zhu C. Chem. Commun. 2012; 48: 979
    • 9n Chen D.-F, Han Z.-Y, He Y.-P, Yu J, Gong L.-Z. Angew. Chem. Int. Ed. 2012; 51: 12307
    • 9o Gronnier C, Kramer S, Odabachian Y, Gagosz F. J. Am. Chem. Soc. 2011; 134: 828
    • 9p Qian D, Zhang J. Chem. Commun. 2012; 48: 7082
    • 9q Luo Y, Ji K, Li Y, Zhang L. J. Am. Chem. Soc. 2012; 134: 17412
    • 9r Shu C, Liu M.-Q, Sun Y.-Z, Ye L.-W. Org. Lett. 2012; 14: 4958
    • 9s Xu M, Ren T.-T, Li C.-Y. Org. Lett. 2012; 14: 4902
    • 9t Fu J, Shang H, Wang Z, Chang L, Shao W, Yang Z, Tang Y. Angew. Chem. Int. Ed. 2013; 52: 4198
    • 10a Li G, Zhang L. Angew. Chem. Int. Ed. 2007; 46: 5156
    • 10b Shapiro ND, Toste FD. J. Am. Chem. Soc. 2007; 129: 4160
    • 10c Davies PW, Albrecht SJ. C. Angew. Chem. Int. Ed. 2009; 48: 8372
    • 10d Li C.-W, Pati K, Lin G.-Y, Sohel SM. A, Hung H.-H, Liu R.-S. Angew. Chem. Int. Ed. 2010; 49: 9891
    • 10e Yeom H.-S, Shin S. Org. Biomol. Chem. 2013; 11: 1089
    • 11a Yeom H.-S, Lee J.-E, Shin S. Angew. Chem. Int. Ed. 2008; 47: 7040
    • 11b Yeom H.-S, Lee Y, Jeong J, So E, Hwang S, Lee J.-E, Lee SS, Shin S. Angew. Chem. Int. Ed. 2010; 49: 1611
    • 11c Mukherjee A, Dateer RB, Chaudhuri R, Bhunia S, Karad SN, Liu R.-S. J. Am. Chem. Soc. 2011; 133: 15372
  • 12 Xiao J, Li X. Angew. Chem. Int. Ed. 2011; 50: 7226
  • 13 He W, Xie L, Xu Y, Xiang J, Zhang L. Org. Biomol. Chem. 2012; 10: 3168
  • 14 Use of 1-ethynyl-2-methylbenzene as the substrate gave indan-1-one; see also ref. 9j. Use of 1-ethynyl-2-methoxy-benzene as the substrate gave 1-benzofuran-3(2H)-one; see also ref. 9t.
  • 15 After submission of this manuscript, Zhang and co-workers reported the synthesis of carboxymethyl ketones from readily available carboxylic acids and terminal alkynes in the presence of a novel gold P,N-bidentate ligand catalyst, see: Ji K, Zhao Y, Zhang L. Angew. Chem. Int. Ed. 2013; 52: 6508
  • 16 Zhou C, Zeng R, Zou J. Chin. J. Chem. 2010; 28: 294
  • 17 Ochiai M, Takeuchi Y, Katayama T, Sueda T, Miyamoto K. J. Am. Chem. Soc. 2005; 127: 12244
  • 18 Kaila N, Janz K, Huang A, Moretto A, DeBernardo S, Bedard PW, Tam S, Clerin V, Keith JC, Tsao DH. H, Sushkova N, Shaw GD, Camphausen RT, Schaub RG, Wang Q. J. Med. Chem. 2007; 50: 40
  • 19 Rubottom GM, Gruber JM. J. Org. Chem. 1978; 43: 1599