Synlett 2019; 30(03): 287-292
DOI: 10.1055/s-0037-1612010
letter
© Georg Thieme Verlag Stuttgart · New York

Dehydrative Allylation of Amine with Allyl Alcohol by Titanium Oxide Supported Molybdenum Oxide Catalyst

a   Interdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan   Email: y-kon@aist.go.jp
,
Takuya Nakashima
a   Interdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan   Email: y-kon@aist.go.jp
,
a   Interdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan   Email: y-kon@aist.go.jp
,
b   Institute for Catalysis, Hokkaido University, N21W10, Sapporo, Hokkaido 001-0021, Japan
c   Research Center for Gold Chemistry, Tokyo Metropolitan University, 1-1-F203 Minami-Osawa, Hachioji, Tokyo 192-0397, Japan
,
b   Institute for Catalysis, Hokkaido University, N21W10, Sapporo, Hokkaido 001-0021, Japan
d   Department of Material and Life Chemistry, Faculty of Engineering, Kanagawa University, 3-27, Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan   Email: uedaw@kanagawa-u.ac.jp
› Author Affiliations
This work was partially supported by the Cooperative Research ­Program of the Institute for Catalysis, Hokkaido University (13A1004).
Further Information

Publication History

Received: 25 October 2018

Accepted after revision: 17 December 2018

Publication Date:
11 January 2019 (online)


Abstract

The dehydrative allylation from allyl alcohol with amines to generate various allyl amines by MoO3/TiO2 solid catalyst is described. The catalyst can be reused at least three times without a decrease of activity.

Supporting Information

 
  • References and Notes

    • 1a Smith MB, March J. In March’s Advanced Organic Chemistry . Wiley-Interscience; New York: 2007. 6th ed. 641
    • 1b Smith MB, March J. In March’s Advanced Organic Chemistry . Wiley-Interscience; New York: 2007. 6th ed. 1672

      Reviews:
    • 2a Muzurt J. Eur. J. Org. Chem. 2007; 3077
    • 2b Tamaru Y. Eur. J. Org. Chem. 2005; 2647
    • 3a Trost BM. Science 1991; 254: 1471
    • 3b Sheldon RA. CHEMTECH 1994; 38
  • 5 Tsuji J. In Palladium Reagents and Catalysts: New Perspectives for the 21st Century. Wiley; Chichester: 2004: 437
  • 6 Kita Y, Sakaguchi H, Hoshimoto Y, Nakauchi D, Nakahara Y, Carpentier J.-F, Ogoshi S, Mashima K. Chem. Eur. J. 2015; 21: 14571
    • 7a Yang S.-C, Hung C.-W. Synthesis 1999; 1747
    • 7b Yang S.-C, Yu C.-L, Tsai Y.-C. Tetrahedron Lett. 2000; 41: 7097
    • 7c Yang S.-C, Tsai Y.-C. Organometallics 2001; 20: 763
    • 7d Kimura M, Futamata M, Shibata K, Tamaru Y. Chem. Commun. 2003; 234
    • 7e van Rijn JA, den Dunnen A, Bouwman E, Drent E. J. Mol. Catal. A: Chem. 2010; 329: 96
    • 7f Banerjee D, Jagadeesh RV, Junge K, Junge H, Beller M. ChemSusChem. 2012; 5: 2039
    • 7g Wagh YS, Sawant DN, Dhake KP, Bhanage BM. Catal. Sci. Technol. 2012; 2: 835
    • 7h Jing J, Hou X, Shen J, Fu J, Meng Q, Zhang W. Chem. Commun. 2017; 53: 5151
    • 7i Masuyama Y, Kagawa M, Kurusu Y. Chem. Lett. 1995; 1122
    • 7j Kinoshita H, Shinokubo H, Oshima K. Org. Lett. 2004; 6: 4085
    • 7k Nishikata T, Lipshutz BH. Org. Lett. 2009; 11: 2377
    • 7l Wang M, Xie Y, Li J, Huang H. Synlett 2014; 25: 2781
    • 7m Gao B, Li L, Zhang G, Huang H. Org. Synth. 2016; 93: 341
    • 7n Hirata G, Satomura H, Kumagae H, Shimizu A, Onodera G, Kimura M. Org. Lett. 2017; 19: 6148
    • 8a Utsunomiya M, Miyamoto Y, Ipposhi J, Ohshima T, Mashima K. Org. Lett. 2007; 9: 3371
    • 8b Mora G, Piechaczyk O, Houdard R, Mezailles N, Le Goff X.-F, le Floch P. Chem. Eur. J. 2008; 14: 10047
  • 9 Qin H, Yamagiwa N, Matsunaga S, Shibasaki M. Angew. Chem. Int. Ed. 2007; 46: 409
  • 10 Das BG, Nallagonda R, Ghorai P. J. Org. Chem. 2012; 77: 5577
  • 11 Shirakawa S, Shimizu S. Synlett 2008; 1539
  • 12 Motokura K, Nakagiri N, Mizugaki T, Ebitani K, Kaneda K. J. Org. Chem. 2007; 72: 6006
  • 13 Kon Y, Fujitani T, Nakashima T, Murayama T, Ueda W. Catal. Sci. Technol. 2018; 8: 4618
  • 14 Details of the preparation of WO3/TiO2, MoO3/TiO2, and ReOn/TiO2 are shown in the Supporting Information.
  • 15 Solid 10 wt%MoO3/TiO2 Catalyst – Typical Preparation for Heterogeneous Catalyst 22 TiO2 P25 (2.00 g) was added to a (NH4)6Mo7O24(H2O)4 (245.3 mg, 0.2 mmol) aqueous solution (1 mL), and the mixed catalyst was dried at 110 °C for 24 h, then calcined at 500 °C for 3 h under air; yield 2.20 g.
  • 16 Dehydrative Allylation of 1 with 2 – Typical Dehydrative Allylation Procedure for Screening of Solid Catalyst A pressure-resistant glass tube equipped with a magnetic stirring bar was loaded with solid catalyst (100 mg), 1 (230 mg, 4.0 mmol), 2 (197 mg, 1.0 mmol), and n-octane (0.25 mL). The vessel was tightly sealed by a screw cap, and the mixture was stirred (500 rpm) in an oil bath maintained at 105 °C for 6 h. After the reaction, the solution was cooled to room temperature and then diluted with 12 mL of acetonitrile. Biphenyl (40 mg, 0.25 mmol) was added to the solution as an internal standard for gas chromatography (GC) analysis. The solution was placed under ultrasonic irradiation for 10 min to ensure a good homogeneity of the mixture. The conversion and yield were determined on the basis of the analysis of the mixture by GC to evaluate catalytic activities. Characterization of 3 was done by 1H NMR and 13C NMR spectra. Characterization details are shown in ref. 16.
  • 17 Ng KY. S, Gulari E. J. Catal. 1985; 92: 340
  • 18 Detection limit of XRD is known to be about 4 nm, and XRD patterns are not observed when the particles are under 4 nm in diameter.
  • 19 Allyl Dibenzyl Amine (3) – Typical Dehydrative Allylation Procedure A pressure-resistant glass tube equipped with a magnetic stirring bar was loaded with MoO3/TiO2 (100 mg), 1 (240 mg, 4.1 mmol), 2 (197 mg, 1.0 mmol), and n-octane (0.25 mL). The vessel was tightly sealed by a screw cap, and the mixture was stirred (500 rpm) in an oil bath maintained at 105 °C for 6 h. The resulting mixture was concentrated and purified by column chromatography (silica gel (100–200 mesh), eluent; n-hexane/ethyl acetate = 50:1) to give a colorless oil; yield: 215 mg (94% isolated yield). Compound 3 17 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.38–7.20 (m, 10 H), 5.96–5.86 (m, 1 H), 5.23–5.13 (m, 2 H), 3.57 (s, 4 H), 3.01–3.09 (m, 2 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ =139.6, 136.0, 128.7, 128.1, 126.8, 117.3, 57.7, 56.3.
    • 20a Matsubara S, Okazoe T, Oshima K, Takai K, Nozaki H. Bull. Chem. Soc. Jpn. 1985; 58: 844
    • 20b Belgacem J, Kress J, Osborn JA. J. Am. Chem. Soc. 1992; 114: 1501
  • 21 Burrington JD, Kartisek CT, Grasselli RK. J. Catal. 1983; 81: 489
  • 22 Vanhove D, Op SR, Fernandez A, Blanchard M. J. Catal. 1979; 57: 253