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

Yoshihiro Kon; Takuya Nakashima; Tadahiro Fujitani; Toru Murayama; Wataru Ueda

doi:10.1055/s-0037-1612010

Synlett, Table of Contents

Synlett 2019; 30(03): 287-292
DOI: 10.1055/s-0037-1612010

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

Yoshihiro Kon *

^aInterdisciplinary 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

^aInterdisciplinary 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

,

Tadahiro Fujitani

^aInterdisciplinary 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

,

Toru Murayama

^bInstitute for Catalysis, Hokkaido University, N21W10, Sapporo, Hokkaido 001-0021, Japan

^cResearch Center for Gold Chemistry, Tokyo Metropolitan University, 1-1-F203 Minami-Osawa, Hachioji, Tokyo 192-0397, Japan

,

Wataru Ueda *

^bInstitute for Catalysis, Hokkaido University, N21W10, Sapporo, Hokkaido 001-0021, Japan

^dDepartment 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

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Abstract

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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.

Key words

allyl amine - molybdenum oxide catalyst - allyl alcohol - titanium oxide - dehydrative allylation

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References

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

Reviews:

4a Sundararaju B, Achard M, Bruneau C. Chem. Soc. Rev. 2012; 41: 4467
4b Bandini M, Cera G, Chiarucci M. Synthesis 2012; 44: 504

5 Tsuji J. In Palladium Reagents and Catalysts: New Perspectives for the 21^st 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 ReO_n/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

Supplementary Material

Supporting Information