New method for the asymmetric reduction of ketophosphonates

Article abstract of DOI:10.1080/10426500701807251

Chiral reducing reactants were prepared from lithium, sodium, or tetrabutylammonium borohydrides and (S)- or (R)-tartaric acids. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426500701807251

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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New Method for the
Asymmetric Reduction of
Ketophosphonates
Vitaly V. Nesterov a & Oleg I. Kolodiazhnyi a
a Institute of Bioorganic Chemistry and
Petrochemistry , National Academy of Sciences of
Ukraine , Kyiv, Ukraine
Published online: 20 Jun 2008.
To cite this article: Vitaly V. Nesterov & Oleg I. Kolodiazhnyi (2008) New Method for
the Asymmetric Reduction of Ketophosphonates, Phosphorus, Sulfur, and Silicon and
the Related Elements, 183:2-3, 687-688, DOI: 10.1080/10426500701807251
To link to this article: http://dx.doi.org/10.1080/10426500701807251
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Phosphorus, Sulfur, and Silicon, 183:687–688, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701807251
New Method for the Asymmetric Reduction
of Ketophosphonates
Vitaly V. Nesterov and Oleg I. Kolodiazhnyi
Institute of Bioorganic Chemistry and Petrochemistry, National
Academy of Sciences of Ukraine, Kyiv, Ukraine
Chiral reducing reactants were prepared from lithium, sodium, or tetrabutylam-
monium borohydrides and (S)- or (R)-tartaric acids.
Keywords Asymmetric redution; chiral phosphonic acids; stereoselectivity
The chiral reducing reactants (S)-1 or (R)-1 were prepared from lithium,
sodium, or tetrabutylammonium borohydrides and (S)- or (R)-tartaric
acids.1,2
The reduction of α- or β-ketophosphonates with (S)- or (R)-1 leads
stereoselectively to the formation of (R)-, or (S)-α- or β-hydroxyphospho-
nates, correspondingly, in high yields and very good stereoselectivity.
The stereoselectivity of reaction depended on the absolute configu-
rations of 1 and ketophosphonates. The reduction of di(1R, 2S, 5R)-
menthyl ketophosphonates with the (R)-1 proceeded with matched
double asymmetric induction to give high enantiomeric excesses of
hydroxyphosphonates (>96% de). The methodology was used for the
preparation of enantiomerically pure phosphonate modified carnitine
and other biologically active phosphonic acids in multigram scale.
Address correspondence to Oleg I. Kolodiazhnyi, Institute of Bioorganic Chem-
istry and Petrochemistry, National Academy of Sciences of Ukraine, Kyiv, Ukraine.
E-mail: oikol123@rambler.ru
687

688
V. V. Nesterov and O. I. Kolodiazhnyi
TABLE I Asymmetric Reduction of Ketophophonates with Reagent
(S)-1 or (R)-1 (RꢀO)2P(O)(CH2)nCH(OH)R
R
R’
N
TA
Yield, %
ee (or de), %
Config.
CH2Cl
CH2Cl
PH
PH
PH
PH
2-FC6H4
2-AN
MNT
ET
ET
MNT
MNT
ET
MNT
MNT
MNT
1
1
0
0
0
0
0
0
0
R, R
R, R
R, R
R, R
S, S
S, S
R, R
R, R
R, R
93
82
95
95
98
94
97
96
97
96
80
60
92.5
46
60
82
74
96
S
S
S
S
R
R
S
S
S
PYPERONYL
REFERENCES
[1] V. V. Nesterov and O. I. Kolodiazhnyi, Tetrahedron: Asymmetry, 17, 1023 (2006).
[2] O. I. Kolodiazhnyi, Tetrahedron: Asymmetry, 16, 3295 (2005).