Synthesis 2016; 48(17): 2837-2844
DOI: 10.1055/s-0035-1561957
special topic
© Georg Thieme Verlag Stuttgart · New York

Reductive Cyclization of 1,6- and 1,7-Enynes Catalyzed by Iron Complexes

Tuo Xi
Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China   Email: luzhan@zju.edu.cn
,
Xu Chen
Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China   Email: luzhan@zju.edu.cn
,
Heyi Zhang
Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China   Email: luzhan@zju.edu.cn
,
Zhan Lu*
Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China   Email: luzhan@zju.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 31 December 2015

Accepted after revision: 26 February 2016

Publication Date:
12 April 2016 (eFirst)

Abstract

Iron-catalyzed reductive cyclization of 1,6- and 1,7-enynes was demonstrated by using an oxazoline iminopyridine ligand. Alcohol, ketone, ester, ether, halide, amine, amide, imine, nitrile, silyl, and alkyne groups are tolerated under the mild reaction conditions. A speculative mechanism is proposed on the basis of deuteration studies. A primary enantioselective transformation was also conducted.

Supporting Information

 
  • References


    • For selected reviews on iron-catalyzed organic transformations, see:
    • 1a Bolm C, Legros J, Le Paih J, Zani L. Chem. Rev. 2004; 104: 6217
    • 1b Sun C.-L, Li B.-J, Shi Z.-J. Chem. Rev. 2011; 111: 1293
    • 1c Gopalaiah K. Chem. Rev. 2013; 113: 3248
    • 1d Jia F, Li Z. Org. Chem. Front. 2014; 1: 194
    • 1e Bauer I, Knölker H.-J. Chem. Rev. 2015; 115: 3170

      For selected reviews on transition-metal-catalyzed cyclization of nonactived 1,6-enynes, see:
    • 2a Trost BM. Acc. Chem. Res. 1990; 23: 34
    • 2b Aubert C, Buisine O, Malacria M. Chem. Rev. 2002; 102: 813
    • 2c Marinetti A, Jullien H, Voituriez A. Chem. Soc. Rev. 2012; 41: 4884

      For selected examples of palladium-catalyzed cyclization of 1,6-enynes, see:
    • 3a Trost BM, Chen S.-F. J. Am. Chem. Soc. 1986; 108: 6053
    • 3b Trost BM, Rise F. J. Am. Chem. Soc. 1987; 109: 3161
    • 3c Trost BM, Lautens M, Chan C, Jebaratnam DJ, Mueller T. J. Am. Chem. Soc. 1991; 113: 636
    • 3d Oh CH, Jung HH, Sung HR, Kim JD. Tetrahedron 2001; 57: 1723
    • 3e Hatano M, Mikami K. J. Am. Chem. Soc. 2003; 125: 4704
    • 3f Corkey BK, Toste FD. J. Am. Chem. Soc. 2007; 129: 2764

    • For selected examples of rhodium-catalyzed cyclization of 1,6-enynes, see:
    • 3g Cao P, Wang B, Zhang X. J. Am. Chem. Soc. 2000; 122: 6490
    • 3h Tong X, Zhang Z, Zhang X. J. Am. Chem. Soc. 2003; 125: 6370
    • 3i Tong X, Li D, Zhang Z, Zhang X. J. Am. Chem. Soc. 2004; 126: 7601
    • 3j Jang H.-Y, Krische MJ. J. Am. Chem. Soc. 2004; 126: 7875
    • 3k Miura T, Shimada M, Murakami M. J. Am. Chem. Soc. 2005; 127: 1094
    • 3l Jang H.-Y, Hughes FW, Gong H, Zhang J.-M, Brodbelt JS, Krische MJ. J. Am. Chem. Soc. 2005; 127: 6174
    • 3m Park JH, Kim SM, Chung YK. Chem. Eur. J. 2011; 17: 10852

    • For selected examples of ruthenium-catalyzed cyclization of 1,6-enynes, see:
    • 3n Trost BM, Toste FD. J. Am. Chem. Soc. 2000; 122: 714
    • 3o Trost BM, Toste FD. J. Am. Chem. Soc. 2002; 124: 5025
    • 3p Trost BM, Surivet J.-P, Toste FD. J. Am. Chem. Soc. 2004; 126: 15592
    • 4a Fürstner A, Martín R, Majima K. J. Am. Chem. Soc. 2005; 127: 12236
    • 4b Fürstner A, Majima K, Martín R, Krause H, Kattnig E, Goddard R, Lehmann CW. J. Am. Chem. Soc. 2008; 130: 1992
    • 5a Sylvester KT, Chirik PJ. J. Am. Chem. Soc. 2009; 131: 8772
    • 5b Hoyt JM, Sylvester KT, Semproni SP, Chirik PJ. J. Am. Chem. Soc. 2013; 135: 4862
  • 6 Lin A.-J, Zhang Z.-W, Yang J. Org. Lett. 2014; 16: 386

    • For Huang’s independent work on chiral oxazoline iminopyridine ligands, see:
    • 7a Zhang L, Zuo Z, Wan X, Huang Z. J. Am. Chem. Soc. 2014; 136: 15501
    • 7b Zuo Z, Zhang L, Leng X, Huang Z. Chem. Commun. 2015; 51: 5073

      For our independent work on chiral oxazoline iminopyridine ligands, see:
    • 8a Chen J, Xi T, Lu Z. Org. Lett. 2014; 16: 6452
    • 8b Chen J, Xi T, Ren X, Guo J, Cheng B, Lu Z. Org. Chem. Front. 2014; 1: 1306
    • 8c Chen J, Cheng B, Cao M, Lu Z. Angew. Chem. Int. Ed. 2015; 54: 4661
    • 8d Guo J, Chen J, Lu Z. Chem. Commun. 2015; 51: 5725
    • 8e Xi T, Mei Y, Lu Z. Org. Lett. 2015; 17: 5939
    • 8f Chen J, Chen C, Ji C, Lu Z. Org. Lett. 2016; 18: 1594
  • 9 Small BL, Brookhart M, Bennett AM. A. J. Am. Chem. Soc. 1988; 120: 4049
  • 10 Wu JY, Moreau B, Ritter T. J. Am. Chem. Soc. 2009; 131: 12915
  • 11 A diethyl malonate-tethered substrate failed to give the corresponding cyclized product in a previous report; see ref. 6.
  • 12 For the unfavorable interaction of the lone pair of the methoxy group with the catalytic center, see: Chen M, Weng Y, Guo M, Zhang H, Lei A. Angew. Chem. Int. Ed. 2008; 47: 2279
  • 13 Sémeril D, Bruneau C, Dixneuf PH. Helv. Chim. Acta 2001; 84: 3335
  • 14 Miura K, Funatsu M, Saito H, Ito H, Hosomi A. Tetrahedron Lett. 1996; 37: 9059