Syntheses of Coniferyl and Sinapyl Alcohols
J. Agric. Food Chem., Vol. 53, No. 9, 2005 3695
aldehydes, but the reaction time is long even when freshly
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(
(
(
(
BER exhibits a high regioselectivity between aldehydes and
ketones, reducing aldehydes more quickly than ketones (20) and
reducing R,â-unsaturated aldehydes without 1,4-reduction (21).
Commercially available BER is strong enough to complete the
required reduction within hours. The products from reduction
of either of the 4-hydroxycinnamaldehydes were remarkably
sinapyl, and p-coumaryl alcohol. J. Agric. Food Chem. 1992,
4
0, 1108-1110.
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1
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coniferyl alcohol 2a product contained ∼0.03% dihydroconiferyl
1
041-1045.
alcohol 3a, and the sinapyl alcohol 2b product contained
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∼0.05% dihydrosinapyl alcohol 3b. There were essentially no
differences between large-scale and small-scale preparations.
Large-scale preparation does not require longer reaction times.
Contaminants from the polymer-supported reagent can be readily
removed from the desired products by simple “plug-filtration”
through silica gel, and no extensive workup is needed. The
products were ready to use without further purification or
crystallization, but both 4-hydroxycinnamyl alcohols can be
recrystallized to enhance their quality and shelf life.
The used resin can be recovered and recycled (21). Because
the resin is relatively nontoxic and nonvolatile, it is easily
handled by nonchemists.
5
35-536.
(
15) Nutaitis, C. F.; Bernardo, J. E. Regioselective 1,2-reduction of
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(16) Saksena, A. K.; Mangiaracina, P. Recent studies on veratrum
alkaloids: a new reaction of sodium triacetoxyborohydride.
Tetrahedron Lett. 1983, 24, 273-276.
(17) Ludley, F. H.; Ralph, J. Improved preparation of coniferyl and
sinapyl alcohols. J. Agric. Food Chem. 1996, 44, 2942-2943.
(18) Lu, F.; Ralph, J. Highly selective syntheses of coniferyl and
sinapyl alcohols. J. Agric. Food Chem. 1998, 46, 1794-1796.
(19) Gibson, H. W.; Baily, F. C. Chemical modification of polymers.
Borohydride reducing agents derived from anion-exchange resins.
J. Chem. Soc., Chem. Commun. 1977, 815.
ACKNOWLEDGMENT
We thank Jane Marita for assistance with GC-MS and also
Mirko Bunzel (University of Hamburg, Germany) and Paul
Schatz for valuable discussions.
(
20) Yoon, N. M.; Park, K. B.; Gyoung, Y. S. Chemoselective
reduction of carbonyl compounds with borohydride exchange
resin in alcoholic solvents. Tetrahedron Lett. 1983, 24, 5367-
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Received for review December 30, 2004. Revised manuscript received
March 4, 2005. Accepted March 15, 2005. We gratefully acknowledge
partial funding through the DOE Energy Biosciences program (No.
DE-AI02-00ER15067) and the USDA-CSREES National Research
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