A new efficient access to glycono-1,4-lactones by oxidation of unprotected itols by catalytic hydrogen transfer with RhH(PPh3)4-benzalacetone system

Article abstract of DOI:10.1055/s-1998-1705

Treatment of unprotected pentitols and hexitols with RhH(PPh₃)₄-benzalacetone system leads exclusively to glycono-1,4-lactones in 60-96% yield.

Full text of DOI:10.1055/s-1998-1705

May 1998
SYNLETT
475
A New Efficient Access to Glycono-1,4-lactones by Oxidation of Unprotected Itols by
Catalytic Hydrogen Transfer with RhH(PPh ) -Benzalacetone System
3 4
I. Isaac, G. Aizel, I. Stasik, A. Wadouachi, D. Beaupère*
Université de Picardie Jules Verne-Laboratoire de Chimie Organique, 33 rue St Leu-80039 Amiens Cédex, France
Received 29 December 1997
Abstract: Treatment of unprotected pentitols and hexitols with
RhH(PPh ) -benzalacetone system leads exclusively to glycono-1,4-
3 4
lactones in 60-96% yield.
The literature records a number of methods for the conversion of diols
to lactones in yields varying from good to poor. These include: silver
1
2
carbonate on Celite, stoichiometric RuCl (PPh ) in benzene, CuSO -
2
3 3
4
3
KMnO , tetrapropylammonium perruthenate-4-methylmorpholine N-
oxide, and catalytic hydrogen transfer (C.H.T) [benzalacetophenone-
RuH (PPh ) ] at 140°C. To our knowledge, the latter is the only
4
4
5
2
3 4
method which has been described to oxidize protected pentitols to
6
afford the corresponding pentonolactones and no method was
applicable for the oxidation of unprotected itols to glyconolactones.
In a previous paper we described the oxidation of protected or
unprotected lactols to glycono-1,4-lactones, in mild conditions, by
C.H.T
with
benzalacetone
as
hydrogen
acceptor
and
7
RhH(PPh ) (hydridotetrakis triphenylphosphine rhodium I) as catalyst.
3 4
We report here the use of this system for the oxidation of unprotected
itols to prepare glycono-1,4-lactones.
As a matter of fact, we observed that treatment of meso erythritol 1 with
RhH(PPh ) (0.2 eq) and benzalacetone (4 eq) in DMF for 3 hours at
3 4
60°C led to the racemic mixture of D,L-erythrono-1,4-lactone 2 in 95%
isolated yield (Scheme 1). This method was also applied to other
unprotected itols (tetritols, pentitols and hexitols) and efficiently yielded
the glycono-1,4-lactones as shown in the Table.
Scheme 1
Pentitols and hexitols which have a plane of symmetry, for example
meso erythritol 1, D-xylitol 8, D-galactitol 18 or a C-2 symmetry axis,
such as D-threitol 3 or D-mannitol 13 led, with good yields, to the
corresponding lactone obtained in a racemic mixture.
Only one exception was observed when D-ribitol 5, having a plane of
symmetry, was oxidized with 0.2 eq of catalyst and 4 eq of
benzalacetone at 60°C for 5 hours. D,L-Ribono-1,4-lactone 6 and D,L-
The oxidation of L-arabinitol which has no symmetry led to the two
expected L-arabinono-1,4-lactone 11 and L-lyxono-1,4-lactone 12 in
72% overall yield and in ratio 11/12=1.25:1.
arabinono-1,4-lactones
7 were isolated in 47% and 18% yield
respectively. Similar epimerisation at C-2 was already observed in the
oxidation of 2-acetamido-2-deoxy-D-mannopyranose with the same
As explained in Scheme 2, after an oxidation at C-1 of L-arabinitol, the
L-arabinopyranose or furanose formed was oxidized to give the L-
arabinono-1,4-lactone 11. The rare L-lyxono-1,4-lactone 12 is obtained
via the L-lyxose resulting from the oxidation at the C-5 of the starting
itol.
8
oxidizing system.
When the oxidation of D-ribitol was performed at 80°C with 0.4 eq of
RhH(PPh ) the overall yield increased to 94% but the ratio 6/7
3 4
remained equal to 2.5:1.

476
LETTERS
SYNLETT
Scheme 2
9
In earlier work, we have shown that RhH(PPh ) induced an
chromatography on silica gel (eluent: AcOEt) gave glycono-1,4-lactone.
All products were identified according to their literature data or their
H, C NMR spectra and their elemental analyses data.
3 4
intramolecular esterification of a dialdehyde derivative. In the case of
itols, it was difficult to assume that a dialdehyde might be the
intermediate, as this hypothesis required the simultaneous oxidation of
the two primary alcohol functions.
1
13
References
Similarly the non symmetric D-glucitol was oxidized to give D-glucono-
1,4-lactone 16, as major product, and the L-gulono-1,4-lactone 17
isolated in 96% overall yield in a ratio 16/17=2.2:1.
(1) Fetizon, M.; Golfier, M.; Louis, J.M. Tetrahedron 1975, 31,171.
(2) Tomioka, H.; Takai, K.; Oshima, K.; Nozaki, H. Tetrahedron Lett.
1981, 22, 1605.
In conclusion, we have shown that oxidation of unprotected itols by
(3) (a) Jefford, C.W.; Wang, Y. J. Chem. Soc. Chem. Comm . 1988,
634; (b) Jefford, C.W.; Li, Y.; Wang, Y. Org. Synth. 1992, 71,
207.
catalytic hydrogen transfer using RhH(PPh ) as catalyst and
3 4
benzalacetone as hydrogen acceptor, afforded preparation of glycono-
1,4-lactones under mild conditions in good yields.
(4) Bloch, R.; Brillet, C. Synlett 1991, 829.
(5) Descotes, G.; Sabadie, J. J. Mol. Catal. 1979, 5, 415.
Typical procedure
(6) Saburi, M.; Ishii, Y.; Kaji, N.; Aoi, T.; Sasaki, I.; Yochikawa, S.;
The RhH(PPh ) catalyst was prepared using the Levinson and
3 4
Uchida, Y. Chem. Lett. 1989, 563.
10
Robinson method.
(7) Isaac, I.; Stasik, I.; Beaupère, D.; Uzan, R. Tetrahedron Lett.
1995, 36, 383.
To a solution of itol (2.5 mmol) and RhH(PPh ) (0.2-0.4 eq) in
3 4
anhydrous DMF (3 mL) at 60-80°C, under argon atmosphere, was
added a solution of benzalacetone (4 eq) in DMF (2 mL). The reduction
of benzalacetone was controlled by GCP ( DEGS, 5%, 10 feet, 160°C).
(8) Isaac, I. Thesis, University of Amiens 1996.
(9) Massoui, M.; Beaupère, D.; Nadjo, L.; Uzan, R. J. Organometal.
Chem. 1985, 259, 345.
After total consumption of the itol [TLC (CHCl -MeOH)],
3
concentration under vacuum gave the crude mixture which was poured
into water and washed with chloroform. The water was evaporated and
(10) Levison, J.J.; Robinson, S.D. J. Chem. Soc. 1970, A, 2947.