Resolution of P-heterocycles with tartaric acid derivatives

Article abstract of DOI:10.1080/10426507.2010.497520

3-Phospholene 1-oxides were efficiently resolved by tartaric acid derivatives. Copyright Taylor & Francis Group, LLC.

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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Resolution of P-Heterocycles with
Tartaric Acid Derivatives
Viktória Ujj a b , Péter Bagi a , Andrea Laki a , Elemér Fogassy a &
György Keglevich a
a Department of Organic Chemistry and Technology , Budapest
University of Technology and Economics (BUTE) , Budapest , Hungary
b Research Group of the Hungarian Academy of Sciences at the
Department of Organic Chemistry and Technology, BUTE , Budapest ,
Hungary
Published online: 25 Apr 2011.
To cite this article: Viktória Ujj , Péter Bagi , Andrea Laki , Elemér Fogassy & György Keglevich (2011)
Resolution of P-Heterocycles with Tartaric Acid Derivatives, Phosphorus, Sulfur, and Silicon and the
Related Elements, 186:4, 792-793, DOI: 10.1080/10426507.2010.497520
To link to this article: http://dx.doi.org/10.1080/10426507.2010.497520
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Phosphorus, Sulfur, and Silicon, 186:792–793, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.497520
RESOLUTION OF P-HETEROCYCLES WITH TARTARIC
ACID DERIVATIVES
Vikto´ria Ujj,1,2 Pe´ter Bagi,1 Andrea Laki,1 Eleme´r Fogassy,1
and Gyo¨rgy Keglevich1
1Department of Organic Chemistry and Technology, Budapest University
of Technology and Economics (BUTE), Budapest, Hungary
2Research Group of the Hungarian Academy of Sciences at the Department
of Organic Chemistry and Technology, BUTE, Budapest, Hungary
Abstract 3-Phospholene 1-oxides were efficiently resolved by tartaric acid derivatives.
Keywords Optical activity; P-heterocycles; resolution
P-Chiral compounds used as ligands are of importance. Preparation and resolution of
racemic phosphine oxides followed by deoxygenation is a practical approach for their
preparation. Five- or six-membered P-heterocycles, such as phospholene oxides (1)
and dihydrophosphinine oxides (2), form a representative class of ring P-compounds
(Scheme 1).
Cl
(1e)
(1f)
(1g)
(1h)
(1a)
(1b)
(1c)
(2a)
(2f)
Y =
Y = Ph
2-MePh
4-MePh
Et
Pr
EtO
2-PrO
Y = Ph
Pr
P
P
1-Naph (1d)
O
Y
O
Y
1
2
Scheme 1
Recently, an efficient method has been developed for the separation of the antipodes of
1-substituted 3-methyl-3-phospholene 1-oxides (1a–h) using a chiral agent, TADDOL [(−)-
3] or spiro-TADDOL [(−)-4]. The racemic phospholene oxides (1a–h) were resolved using
half equivalent of reagent (−)-3 or (−)-4 and in most cases 1:1 crystalline diastereomeric
complexes were formed that were purified by recrystallization and the enantiomers of 1
were recovered by flash column chromatography (Scheme 2). From among the phospholene
oxides (1) obtained, seven species could be resolved with an ee of >95%.1
Received 26 May 2010; accepted 26 May 2010.
Support from the Hungarian Scientific Research Fund (OTKA No. K075236, K067679, K83118) is ac-
knowledged.
Address correspondence to Gyo¨rgy Keglevich, Department of Organic Chemistry and Technology, Budapest
University of Technology and Economics (BUTE), P.O. Box 91, Budapest 1521, Hungary. E-mail: gkeglevich@
mail.bme.hu
792

RESOLUTION OF P-HETEROCYCLES
793
R
O
R
O
R
O
R
O
R = Me R =
R = Me R =
.
2
+
+
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
P
P
P
O
Y
O
Y
O
Y
OH HO
[1 (−)−3] or [1 (−)−4]
OH HO
(−)−3 or (−)−4
.
.
1
1
Scheme 2
We have described another convenient method for the resolution of phospho-
lene oxides 1a–h with calcium hydrogen (−)-(2R,3R)-O,Oꢁ-dibenzoyl-tartrate [(−)-Ca(H-
DBTA)2, (−)-5] or (−)-(2R,3R)-O,Oꢁ-di(p-toluyl)-tartrate [(−)-Ca(H-DPTTA)2, (−)-6] via
diastereomeric coordination complex formation. Phospholene oxides 1a–h were crystal-
lized with 0.25 equivalent of resolving agent [(−)-5 or (−)-6] and, in most cases, the
composition of the precipitated complexes was the same [Ca(1)2(TA#)2] (where TA# is
H-DBTA or H-DPTTA; Scheme 3). The complexes were further purified by digestion,
and then the enantiomers of phospholene oxides 1a–h were recovered by treatment with
aqueous ammonia to afford six phospholene oxides (1) with an ee of >90%.2
OOCAr
H
OOCAr
H
H
H
4
Ca2+
Ca2+
+ 2
+
ArCOO
HOOC
ArCOO
HOOC
COO−
COO−
P
P
P
2
n
2
O
O
Y
O
Y
Y
n = 2
exceptions:
n = 1, Y = Pr, Ar = Ph
n = 1, Y = Ph, Ar = p-MePh
1
(–)–5 Ar = Ph
(–)–6 Ar = p-MePh
Scheme 3
The resolution method was extended for the resolution of 1-phenyl-1,2-
dihydrophosphinine oxide (2a) using spiro-TADDOL [(−)-4]3 and for that of 1-
propyl-1,2-dihydrophosphinine oxide (2f) using [(−)-Ca(H-DBTA)2, (−)-5]. The new
optically active phospholene oxides (1) may serve, after deoxygenation, as novel P-ligands
in transition-metal complexes.
REFERENCES
1. Nova´k, T.; Ujj, V.; Schindler, J.; Czugler, M.; Kubinyi, M.; Mayer, Z. A.; Fogassy, E.; Keglevich,
G. Tetrahedron: Asymmetry 2007, 18, 2965–2972.
2. Ujj, V.; Schindler, J.; Nova´k, T.; Czugler, M.; Fogassy, E.; Keglevich, G. Tetrahedron: Asymmetry
2008, 19, 1973–1977.
3. Ujj, V.; Kere´nyi, A.; Laki, A.; Fogassy, E.; Keglevich, G. Lett. Org. Chem. 2010, 7, 110–113.