Toward the synthesis of (+)-pericosine B

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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Toward the Synthesis of (+)-
Pericosine B
José L. García Ruano a , Jesús López-Cantarero a
Carlos Alemparte a
&
a Departamento de Química Orgánica, Universidad
Autónoma de Madrid , Madrid, Spain
Published online: 16 Aug 2006.
To cite this article: José L. García Ruano , Jesús López-Cantarero & Carlos Alemparte
(2005) Toward the Synthesis of (+)-Pericosine B, Phosphorus, Sulfur, and Silicon and
the Related Elements, 180:5-6, 1493-1494, DOI: 10.1080/10426500590913339
To link to this article: http://dx.doi.org/10.1080/10426500590913339
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Phosphorus, Sulfur, and Silicon, 180:1493–1494, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500590913339
Toward the Synthesis of (+)-Pericosine B
´
´
Jose L. Garcıa Ruano
´
´
Jesus Lopez-Cantarero
Carlos Alemparte
Departamento de Qu´ımica Orga´nica, Universidad Auto´noma de Madrid,
Madrid, Spain
Keywords Asymmetric synthesis; Diels–Alder reaction; natural products; sulfoxides
INTRODUCTION
(+)-Pericosine B, a marine natural product isolated from a strain of
Periconia byssoides,1 is an attractive synthetic target because of its sig-
nificant activity in the P388 lymphocytic leukemia test system. The
only reported synthesis of this compound2 involves the use, as a cru-
cial step, of a poorly stereoselective dihydroxylation (de = 38%) with
stoichiometric amounts of highly toxic and expensive OsO4.
RESULTS
In this communication, we describe a new enantioselective syn-
thesis of (+)-Pericosine B based on the Diels–Alder reaction of 3-
sulfinylacrylonitrile (1) with furan3 as the key step.
Received July 9, 2004; accepted October 5, 2004.
Address correspondence to Jesu´s Lo´pez Cantarero, Departamento de Qu´ımica
Orga´nica, Universidad Auto´noma de Madrid, Cantoblanco, 28049 Madrid, Spain. E-mail:
jesus.cantarero@uam.es
1493

1494
J. L. Garc´ıa Ruano et al.
Dihydroxylation and protection of cycloadduct 2 afforded compound
3, which easily evolved into the α,β-unsaturated nitrile 4 upon basic
treatment. This interesting chiral synthon allows the introduction of
nucleophiles at C-6 in a stereoselective manner. Thus, its reaction with
MeOH, followed by concomitant oxabridge-opening and deprotection,
gave nitrile 6, the immediate precursor of (+)-Pericosine B. Compound
4 also provided access to Shikimic acid derivatives such as 5.
It must be pointed out that the role of the sulfinyl group in this
synthesis is double, as a chiral auxiliary in the key Diels–Alder reaction
and as a precursor of the double bond required for the conjugate addition
of methanol.
REFERENCES
[1] A. Numata, M. Iritani, T. Yamada, K. Minoura, E. Matsumura, T. Yamori, and
T. Tsuruo, Tetrahedron Lett., 38, 8215 (1997).
[2] T. J. Donohoe, K. Blades, M. Helliwell, M. J. Waring, and N. J. Newcombe, Tetrahedron
Lett., 39, 8755 (1998).
[3] J. L. Garc´ıa Ruano, C. Alemparte, A. M. Mart´ın Castro, H. Adams, and J. H. Rodr´ıguez
Ramos, J. Org. Chem., 65, 7938 (2000).