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under Ar. Other reagents were obtained commercially and were
used without further purification.
Keywords: biomass · bis(hydroxymethyl)furan · formic acid ·
hydroxymethylfufural · transfer hydrogenation
Dehydration of d-fructose: d-fructose (3.6 g, 20 mmol), solvent (see
Table 1), and formic acid (0.088 mL, 2.0 mmol) were charged to a
medium-pressure reactor, which was heated to the desired temper-
ature. Reaction progress was monitored by 1HNMR spectroscopy.
Transfer hydrogenation of HMF: Formic acid (0.088 mL, 2.0 mmol)
in THF (2 mL) was dispensed from a syringe pump (flow rate=
2 mLhÀ1) into a 50 mL flask containing HMF (0.25 g, 2.0 mmol),
THF (3 mL), and iridium or ruthenium catalyst (0.001–0.02 mmol) at
408C. In situ NMR characterization confirmed quantitative conver-
sion of HMF to BHMF after the addition was complete. Solvent and
low-boiling compounds were removed under vacuum, yielding
BHMF as yellow powder. Isolated yield of BHMF: 0.24 g(94%).
Ed. 2006, 45, 696–698; c) M. Mascal, E. B. Nikitin, Angew. Chem. 2008,
120, 8042–8044; Angew. Chem. Int. Ed. 2008, 47, 7924–7926.
[2] a) D. F. M. Kuster, Starch/Staerke 1990, 42, 314–321; b) J. B. Binder, R. T.
Raines, J. Am. Chem. Soc. 2009, 131, 1979–1985; c) H. Zhao, J. E. Holla-
day, H. Brown, Z. C. Zhang, Science 2007, 316, 1597–1600; d) C. Lansa-
lot-Matras, C. Moreau, Catal. Commun. 2003, 4, 517–520.
[3] T. Thananatthanachon, T. B. Rauchfuss, Angew. Chem. 2010, DOI:
10.1002/ange.201002267; Angew. Chem. Int. Ed. 2010, 10.1002/
anie.201002267.
[4] a) H. Mehdi, V. Fabos, R. Tuba, A. Bodor, L. T. Mika, I. T. Horvath, Top.
Catal. 2008, 48, 49–54; b) I. T. Horvꢂth, H. Mehdi, V. Fꢂbos, L. Boda, L. T.
Mika, Green Chem. 2008, 10, 238–242.
[5] Y. Romꢂn-Leshkov, C. J. Barrett, Z. Y. Liu, J. A. Dumesic, Nature 2007, 447,
982–985.
[6] S. Goswami, S. Dey, S. Jana, Tetrahedron 2008, 64, 6358–6363.
[7] A. S. Mamman, J. M. Lee, Y. C. Kim, I. T. Hwang, N. J. Park, Y. K. Hwang,
J. S. Chang, J. S. Hwang, Biofuels, Bioprod. Biorefin. 2008, 2, 438–454.
[8] C. Sievers, M. B. Valenzuela-Olarte, T. Marzialetti, D. Musin, P. K. Agrawal,
C. W. Jones, Ind. Eng. Chem. Res. 2009, 48, 1277–1286.
[9] a) M. J. Earle, K. R. Seddon, Pure Appl. Chem. 2000, 72, 1391–1398; b) R.
Sheldon, Chem. Commun. 2001, 2399–2407.
[10] a) T. P. Thuy Pham, C. E. Cho, Y. S. Yun, Water Res. 2010, 44, 352–372;
b) P. J. Scammells, J. L. Scott, R. D. Singer, Aust. J. Chem. 2005, 58, 155–
169.
One-pot synthesis of BHMF: d-fructose (3.6 g, 20 mmol), DMSO
(1 mL), THF (10 mL), and formic acid (0.088 mL, 2.0 mmol) were
charged to a medium-pressure reactor, which was heated to 1508C
for 5 h. NEt3 (0.28 mL, 2 mmol) and iridium catalyst (0.1 mmol)
were added to the HMF solution. The solution was stirred at 408C
for 5 min before a solution of formic acid (0.88 mL, 20 mmol) in
THF (20 mL) was added using a syringe pump (flow rate=
2.5 mLhÀ1). The cooled reaction mixture was transferred into a
250 mL flask containing 50 mL H2O. THF was removed under pres-
sure, and the remaining solution was extracted with ether (4ꢁ
50 mL). Evaporation of the dried ether extract afforded an orange
oil of BHMF, which solidified at À208C. Yield of BHMF: 1.82 g
(71%).
One-pot synthesis of furfuryl alcohol: d-xylose (3.0 g, 20 mmol),
DMSO (1 mL), THF (10 mL), and formic acid (0.088 mL, 2.0 mmol)
were charged to a medium-pressure reactor, which was heated to
1508C for 7 h. NEt3 (0.28 mL, 2 mmol) and iridium catalyst
(0.1 mmol) were added to the HMF solution. The solution was
stirred at 408C for 5 min before formic acid (0.88 mL, 20 mmol) in
THF (20 mL) was added using a syringe pump (flow rate=
2.5 mLhÀ1). The solution was poured into a 250 mL round-bottom
flask containing 50 mL H2O. THF was removed under pressure and
the remaining solution was extracted with ether (4ꢁ50 mL). Furfur-
yl alcohol was obtained as orange liquid after drying the organic
layer under pressure. Isolated yield of furfuryl alcohol: 1.10 g
(63%).
[11] a) Y. Romꢂn-Leshkov, J. N. Chheda, J. A. Dumesic, Science 2006, 312,
1933–1937; b) J. N. Chheda, J. A. Dumesic, Catal. Today 2007, 123, 59–
70.
[12] a) T. Ikariya, A. J. Blacker, Acc. Chem. Res. 2007, 40, 1300–1308; b) R.
Noyori, S. Hashiguchi, Acc. Chem. Res. 1997, 30, 97–102.
[13] M. L. Clark, G. F. Roff, Handbook of Homogeneous Hydrogenation, Wiley-
VCH, Weinheim 2007.
[14] S. Arita, T. Koike, Y. Kayaki, T. Ikariya, Organometallics 2008, 27, 2795–
2802.
[15] K. Murata, T. Ikariya and R. Noyori, J. Org. Chem. 1999, 64, 2186–2187.
[16] a) Z. Srokol, A. Bouche, A. van Estrik, R. C. J. Strik, T. Maschmeyer, J. A.
Peters, Carbohydr. Res. 2004, 339, 1717–1726; b) H. E. van Dam, A. P. G.
Kieboom, H. van Bekkum, Starch/Staerke 1986, 38, 95–101.
[17] a) F. Joꢃ, ChemSusChem 2008, 1, 805–808; b) S. Enthaler, ChemSusChem
2008, 1, 801–804; c) R. Tanaka, M. Yamashita, K. Nozaki, J. Am. Chem.
Soc. 2009, 131, 14168–14169.
Catalyst Stability Studies: A solution of iridium catalyst (0.02 mmol)
and FA (7.7 mL, 0.2 mmol) in [D6]DMSO (1 mL) was monitored by
1HNMR spectroscopy at 208C. Decomposition was indicated by
changes in the Cp* signal (d=1.78 ppm) for the starting catalyst.
[18] Z. M. Heiden, T. B. Rauchfuss, J. Am. Chem. Soc. 2007, 129, 14303–
14310.
[19] K. J. Haack, S. Hashigushi, A. Fujii, T. Ikariya, R. Noyori, Angew. Chem.
1997, 109, 297–300; Angew. Chem. Int. Ed. Engl. 1997, 36, 285–288.
Acknowledgements
This work was supported by British Petroleum through the
Energy Biosciences Institute and in part by the Department of
Energy.
Received: July 9, 2010
Published online on August 23, 2010
ChemSusChem 2010, 3, 1139 – 1141
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1141