In conclusion, the biphasic reaction could be operated using
aqueous 1,3-propanediol produced by fermentation of either
pure or crude glycerol after removal of the cells but without
further purification of the fermentation broth. The product
distribution depended on the purity of the glycerol used as the
initial fermentation substrate.
3 H.-J. Huang, S. Ramaswamy, U. W. Tschirner and
B. V. Ramarao, Sep. Purif. Technol., 2008, 62, 1.
4
5
A. Bruggink, R. Schoevaart and T. Kieboom, Org. Process Res.
Dev., 2003, 7, 622.
(a) M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi and
C. D. Pina, Angew. Chem., Int. Ed., 2007, 46, 4434; (b) A. Behr,
J. Eilting, K. Irawadi, J. Leschinski and F. Lindner, Green Chem.,
2008, 10, 13; (c) C.-H. Zhou, J. N. Beltramini, Y.-X. Fana and
G. Q. Lu, Chem. Soc. Rev., 2008, 37, 527.
6 E. Petitdemange, C. Durr, S. A. Andaloussi and G. Raval, J. Ind.
Microbiol., 1995, 15, 498.
It would be desirable to operate a fully integrated
2
0
bio-chemocatalytic process. Toluene is a biocidal solvent,
and is unsuitable for use in an integrated one pot cascade.
Toluene was substituted with the ionic liquid, methyl trioctyl-
7
8
9
M. Gonzalez-Pajuelo, J. C. Andrade and I. Vasconcelos, J. Ind.
Microbiol. Biotechnol., 2004, 31, 442.
S. Papanikolaou, P. Ruiz-Sanchez, B. Pariset, F. Blanchard and
M. Fick, J. Biotechnol., 2000, 77, 191.
S. Papanikolaou, M. Fick and G. Aggelis, J. Chem. Technol.
Biotechnol., 2004, 79, 1189.
ammonium bistriflamide (N1,8,8,8NTf
has been used in other biphasic microbial processes.
the amination was performed in N1,8,8,8NTf at 115 1C using
2
), since the latter solvent
2
1–25
When
2
the supernatant from fermentation of pure glycerol, 11%
conversion in 24 h afforded products 2 and 3. Thus, the
selectivity was shifted towards dehydration and reduction of
the monoaminated product 1.
1
0 C. E. Nakamura and G. M. Whited, Curr. Opin. Biotechnol., 2003,
14, 454.
11 J. J. Malinowski, Biotechnol. Tech., 1999, 13, 127.
1
1
2 R. V. Oppenauer, Recl. Trav. Chim. Pays-Bas, 1937, 56, 137.
3 F. Hanasaka, K. Fujita and R. Yamaguchi, Organometallics, 2004,
Since the biocatalyst operates only at temperatures o42 1C,
the catalytic reaction was tested at lower temperatures. When
the 1,3-propanediol had been produced by fermentation of pure
glycerol, only 7 and 2% of the substrate was converted after
reacting for 48 h at 60 and 42 1C, respectively. However,
the selectivity was shifted entirely towards N-propyl aniline
formation. The conversion was improved when the culture
supernatant from fermentation of crude glycerol was used as
the source of 1,3-propanediol. Conversions of 12 and 10% were
achieved at 60 and 42 1C, respectively (Table 3). Again, the only
detected product was N-propyl aniline. Overall 3 was the
favoured product at lower conversion and lower temperatures
in the aqueous/ionic liquid biphasic reaction medium. Further
studies are underway to assess the scope of this transformation,
and to optimise the reaction conditions. We are also investigating
methods to recover and re-use the catalyst.
2
3, 1490.
14 (a) C. F. Winans and H. Adkins, J. Am. Chem. Soc., 1932, 54, 306;
b) M. V. Klyuev and M. L. Khidekel, Russ. Chem. Rev. (Engl.
(
Transl.), 1980, 49, 14; (c) R. Grigg, T. R. B. Mitchell,
S. Sutthivaiyakit and N. Tongpenyai, J. Chem. Soc., Chem.
Commun., 1981, 611; (d) Y. Tsuji, R. Takeuchi, H. Ogawa and
Y. Watanabe, Chem. Lett., 1986, 293; (e) D. M. Roundhill, Chem.
Rev., 1992, 92, 1; (f) K.-i. Fujita, Z. Li, N. Ozeki and
R. Yamaguchi, Tetrahedron Lett., 2003, 44, 2687; (g) H. S.
A. Hamid, P. S. Slatford and J. M. J. Williams, Adv. Synth. Catal.,
2007, 349, 1555, and reference therein; (h) A. P. Da Costa,
M. Viciano, M. Sana u´ , S. Merino, J. Tejeda, E. Peris and
B. Royo, Organometallics, 2008, 27, 1305.
5 (a) R. N. Salvatore, C. H. Yoon and K. W. Jung, Tetrahedron,
1
1
2
001, 57, 7785; (b) M. Breuer, K. Ditrich, T. Habicher, B. Hauer,
M. Kesseler, R. Stuermer and T. Zelinski, Angew. Chem., Int. Ed.,
004, 43, 788.
2
6 H. Biebl, K. Menzel, A. P. Zeng and W. D. Deckwer, Appl.
Microbiol. Biotechnol., 1999, 52, 289.
17 C. butyricum DSM10703 was grown anaerobically in modified Y5
18
We have demonstrated that a one pot bio- and chemo-
catalytic process can be used for direct conversion of crude
glycerol to valuable secondary amines in a biphasic system
without intermediate separation of 1,3-propanediol. The
reaction conditions for the biological and chemocatalytic
reactions are remarkably convergent with respect to solvents,
temperature and pressure, offering excellent prospects for
future development of a fully integrated process.
medium at 35 1C and pH 6.5. Pure or crude glycerol was added to
2
tions of fermentation products were measured by HPLC. Further
À1
0 g L . Initial and final glycerol concentrations and concentra-
details are provided in ESIw.
18 M. Rebros, N. Gunaratne, J. Ferguson, K. R. Seddon and
G. Stephens, Green Chem., 2009, 11, 402.
1
9 (a) R. Corbera, M. Sanau and E. Peris, J. Am. Chem. Soc., 2006,
28, 3974; (b) A. C. Marr, C. L. Pollock and G. C. Saunders,
Organometallics, 2007, 26, 3283.
20 C. L. Woldringh, J. Bacteriol., 1973, 114, 1359.
1
2
2
2
1 H. Pfruender, M. Midjojo, U. Kragl and D. Weuster-Botz, Angew.
Chem., Int. Ed., 2004, 43, 4529.
We thank the EPSRC Life Science Interface Programme for
financial support via grants EP/E010636/1 and EP/E010687/1.
2 H. Li, P. Williams, J. Micklefield, J. M. Gardiner and G. Stephens,
Tetrahedron, 2004, 60, 753.
Notes and references
3 M. F. Rodriguez Martinez, N. Kelessidou, Z. Law, J. Gardiner
and G. Stephens, Anaerobe, 2008, 14, 55.
1
(a) P. Gallezot, Green Chem., 2007, 9, 295; (b) R. Luque,
L. Herrero-Davila, J. M. Campelo, J. H. Clark, J. M. Hidalgo,
D. Luna, J. M. Marinas and A. A. Romero, Energy Environ. Sci.,
24 H. Korbekandi, P. Mather, J. Gardiner and G. Stephens, Enzyme
Microb. Technol., 2008, 42, 308.
2008, 1, 542.
Z.-L. Xiu and A.-P. Zeng, Appl. Microbiol. Biotechnol., 2008, 78, 917.
25 R. J. Cornmell, C. L. Winder, S. Schuler, R. Goodacre and
G. Stephens, Green Chem., 2008, 10, 685.
2
2
310 | Chem. Commun., 2009, 2308–2310
This journal is ꢀc The Royal Society of Chemistry 2009