Double asymmetric induction as method for the synthesis of chiral organophosphorus compounds

Article abstract of DOI:10.1080/10426500213410

New examples of multistereoselective syntheses of organophosphorus compounds are described.

Full text of DOI:10.1080/10426500213410

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Double Asymmetric Induction as Method for
the Synthesis of Chiral Organophosphorus
Compounds
Oleg I. Kolodiazhnyi
To cite this article: Oleg I. Kolodiazhnyi (2002) Double Asymmetric Induction as Method for the
Synthesis of Chiral Organophosphorus Compounds, Phosphorus, Sulfur, and Silicon and the
Related Elements, 177:8-9, 2111-2114, DOI: 10.1080/10426500213410
To link to this article: http://dx.doi.org/10.1080/10426500213410
Published online: 27 Oct 2010.
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Date: 25 June 2016, At: 04:44

Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2111–2114
Copyright �C 2002 Taylor & Francis
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042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290094837
DOUBLE ASYMMETRIC INDUCTION AS METHOD
FOR THE SYNTHESIS OF CHIRAL
ORGANOPHOSPHORUS COMPOUNDS
Oleg I. Kolodiazhnyi
National Academy of Sciences of Ukraine, Ukraine
(Received July 29, 2001; accepted December 25, 2001)
New examples of multistereoselective syntheses of organophosphorus
compounds are described.
Keywords: Asymmetric Michael addidion; chiral aminophosphonic
acids; chiral phosphoric acid esters; double asymmetric synthesis;
multistereoselectivity
Multistereoselectivity is the reaction process proceeding under the con-
trol of several chiral auxiliaries effecting the asymmetric induction.
Stereoselectivity of reagents can be estimated as a difference of reaction
rates or activation energies leading to two opposite stereoisomers.1
The individual diastereofacial preferences of the two chiral reactants
may reinforce one another (matched asymmetric synthesis (AS)), or, on
the contrary, oppose one another (mismatched AS).
,2
In the present work the following versions of multistereoselective
syntheses have been studied:
r
a chiral reagent reacts with a chiral substratum;
a chiral reagent containing two chiral auxiliaries reacts with an achi-
ral substratum; and
AS of a chiral reagent in the presence of asymmetric catalyst.
r
r
Thus, the addition of chiral di-and trialkylphosphites
(
R*O = Menthyl, Bornyl, Gluco-D-furanosyl) to chiral C N compounds
is accompanied by double asymmetric induction at the �-carbon atom,
This work is supported by the State Foundation of Basic Research of Ukraine (DFFD).
Address correspondence to Oleg I. Kolodiazhnyi, Institute of Bioorganic Chemistry,
National Academy of Sciences of Ukraine, Murmanska, 1, Kyiv, 02094, Ukraine. E-mail:
oikol123@bpci.kiev.ua
2
111

2
112
O. I. Kolodiazhnyi
FIGURE 1
with formation of optically active aminophosphonic acid ethers of
100% de in case of reagents having matched asymmetric induction
�
and of 80% de in case of reagents possessing mismatched asym-
metric induction. The reaction of di- and trimenthylphosphites gives
aminophosphonic acids of opposite configuration, that allows to prepare
all four possible diastereomers. The menthyl esters by acidic hydrolysis
were converted to N-substituted aminophosphonic acids and then by
catalytic hydrogenation under Pd/C to 1-aminobenzylphosphonic
acids.3
,4
Addition of chiral esters of trivalent phosphorus acids to chiral esters
of crotonic or cinnamic acids proceeds more stereoselectively than in
5
the case when only one of these reagents is chiral. The reaction of
dimenthyl phosphite with menthyl crotonoate proceeds with � 96–98%
2
,5
stereoselectivity.
FIGURE 2

Double Asymmetric Induction
2113
FIGURE 3
The addition of nitrostyrene to trimenthylphosphite leads to
the formation of optically active �-nitroalkylphosphonates and �-
2
aminophoshonic acids 3,5.
Reduction of dimenthyl acylphosphonate with LiAlH4 or NaBH4 af-
fords a mixture of chiral (R)- and (S)-diastereomers in the ratio of
5
�
3:1. Meantime catalytic hydrogenation of the acylphosphonate by
complex of lithium alumohydride with chiral ligand (A = cinchonin or
cyclohexylidene 1,2-gluco-D-furanose) furnishs predominantly one di-
astereomer of dimenthyl 1-oxybenzylphosphonic acid.5
This diastereoface selectivity is explained by effect of menthyl group
of the compounds which closes one of the sides of carbonyle group in
such a manner that Si-side of ketone is shielded more than Re-party
and lithium alumohydride attacks preferentially this side.
Chiral reagents containing two asymmetric auxiliaries in one
molecule, increasing asymmetric induction, are especially interesting.6
Thus, the lithium derivative of Schiff base, formed from (R)- cam-
phor and diethyl aminomethanephosphonate, was allowed to react with
alkyl and benzyl halides to yield the corresponding esters of (S)-�-
aminoalkanephosphonic acids.
Acidolysis of the chiral di-alkylaminophosphines by formic acid
leads in good yield to the formation of optically pure phosphonic acid
amides.7
� 9
So multistereoselectivity represents effective methodology to in-
crease the asymmetric synthesis of chiral organophosphorus com-
pounds using in one reaction two or three asymmetric auxiliaries
FIGURE 4

2
114
O. I. Kolodiazhnyi
FIGURE 5
FIGURE 6
reinforcing one another. In some cases this methodology allows to in-
crease the stereoselectivity of reactions up to 100% de.
REFERENCES
[1] O. I. Kolodiazhnyi, Tetrahedron: Asymmetry (Report N 35), 9, 1279–1332 (1998).
[2] A. Horeau, H. Kagan, and J.-P. Vigneron, Bull. Chem. Soc. France, 3795 (1968).
[3] O. I. Kolodiazhnyi, S. Yu. Sheiko, and E. V. Gryshkun, Heteroatom Chem., 11, 138–143
(2000).
[
[
[
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5] S. Sheiko, Ph.D. Dissertation, Kyiv (2001), p. 120.
6] V. P. Kukhar and H. Hudson. (Eds.), Aminophosphonic and Aminophosphinic Acids.
Chemistry and Biological Activity (John Wiley & Sons, 2000), p. 127.
[
[
[
7] O. I. Kolodiazhnyi and N. Prynada-Andrushko, Tetrahedron Lett., 41, 7997–8000
(
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2001).
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(