The tert-butylaminomethyl(mesityl)phosphinic acid ester and formation of its zinc dichloride complex: Syntheses and characterization

Article abstract of DOI:10.1515/mgmc-2018-0014

The syntheses and structures of tert-butylaminomethyl(mesityl)phosphinic acid ethyl ester 2 and its zinc dichloride complex 3 are reported. In the solid state, both compounds are dimeric via hydrogen bridges. In the complex 3, the phosphinic acid ester 2

Full text of DOI:10.1515/mgmc-2018-0014

Main Group Met. Chem. 2018; aop
Michael Lutter, Lukas M. Stratmann and Klaus Jurkschat*
The tert-butylaminomethyl(mesityl)phosphinic
acid ester and formation of its zinc dichloride
complex: syntheses and characterization
https://doi.org/10.1515/mgmc-2018-0014
Results and discussion
Received March 24, 2018; accepted April 25, 2018
Abstract: The syntheses and structures of tert- The tert-butylaminomethyl(mesityl)phosphinic acid
butylaminomethyl(mesityl)phosphinic acid ethyl ester 2 ethyl ester tert-Bu(H)NCH2(2,4,6-Me3C6H2)P(O)OEt, 2, was
and its zinc dichloride complex 3 are reported. In the solid obtained as its racemate through the amination reaction
state, both compounds are dimeric via hydrogen bridges. of compound 1 with an excess of tert-butylamine accord-
In the complex 3, the phosphinic acid ester 2 coordinates ing to Equation 1.
the zinc dichloride diastereoselectively.
O
O
P∗ OEt
P∗ OEt
2tBuNH2
− tBuNH3I
Mes
Mes
Keywords: chelate ligand; diastereoselectivity; phos-
phinic acid ester; phosphorus; zinc.
(1)
I
NH
tBu
1
2, 65%
Introduction
The reaction was performed under elevated pressure at
65°C in a teflon-sealed tube. In the course of the reaction,
the precipitated white solid was identified by means of
the melting point as tert-butylammonium iodide (220°C,
lit. 218–220°C (Herrschaft and Hartl, 1989). After a reac-
tion time of 96 h, the conversion was complete and the
reaction mixture was purified by performing acid base
extraction. Compound 2 was obtained as a white solid
material with a melting point of 67°C. A 31P{1H} NMR spec-
trum of its solution in CDCl3 showed a singlet resonance
at δ 44.6 ppm that was low field shifted as compared with
the signal of compound 1 [δ 38.0 ppm, CDCl3 (Lutter and
Diorganophosphinic acids R2PO2H (Rꢀ=ꢀalkyl, aryl) are a
fundamental class of phosphorus compounds. Together
with their esters R2PO2R′ and the corresponding anions
R2PO2− they are rather popular phosphorus-based ligands
in both main group and transition metal chemistry.
The structural diversity of their metal complexes with a
total number of more than 500 solid state structures has
recently been reviewed (Carson et al., 2017). To the best of
our knowledge, unsymmetrically substituted alkyl(aryl)-
phosphinic acids and their corresponding derivatives
(Korpiun et al., 1968; Onyido et al., 2005) as well as
functionally substituted compounds have also received
increased interest (Maier, 1992; Kaboudin et al., 2006;
Demkowicz et al., 2016). Metal complexes with ligands
containing phosphinic acid moieties have been reported
as well (Lukeš et al., 2001; Cao et al., 2011; Ševčík et al.,
2014). Herein, we present an organoaminomethyl(aryl)-
phosphinic acid ester and demonstrate its behavior as a
chelate ligand towards zinc dichloride.
1
Jurkschat, 2018)]. A H NMR spectrum revealed the char-
acteristic singlet resonance of the tert-butyl protons at
δ 0.89 ppm. An electrospray ionization (ESI) mass spec-
trum showed three mass clusters which were assigned to
+
+
+
[2 2ꢀ+ꢀNa] (m/zꢀ=ꢀ617.3), [2ꢀ+ꢀNa] (m/zꢀ=ꢀ320.1) and [2ꢀ+ꢀH]
(m/zꢀ=ꢀ298.1). From its solution in acetone, colorless
block-shaped crystals of compound 2 were obtained; the
compound crystallized in the monoclinic space group
P21/n with four molecules in the asymmetric unit (Figure
1). Hydrogen bond distances and angles are given in the
Figure caption. Crystallographic data are given in Table 1.
There exists a hydrogen bond (N1-H1ꢀ·ꢀ·ꢀ·ꢀO1 3.001(3) Å,
170(3)°) between the PO and NH functional groups con-
necting two molecules. In the graph set analysis accord-
ing to Etter and Bernstein (Bernstein et al., 1990, 1995a,b;
Etter, 1990, 1991; Etter et al., 1990; Bernstein, 1991) the
unitary elemental graph set is N1 = R22 (10), which is a
*Corresponding author: Klaus Jurkschat, Lehrstuhl fur Anorganische
Chemie II, Technische Universität Dortmund, Otto-Hahn-Straße 6,
D-44221 Dortmund, Germany,
e-mail: klaus.jurkschat@tu-dortmund.de
Michael Lutter and Lukas M. Stratmann: Lehrstuhl fur Anorganische
Chemie II, Technische Universität Dortmund, Otto-Hahn-Straße 6,
D-44221 Dortmund, Germany
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2ꢀ ꢀM. Lutter et al.: Diorganophosphinic acid ester and its zinc complex
ten-membered ring motif. In order to investigate the prop-
erties of compound 2 as a chelating ligand, the latter was
reacted with zinc chloride in acetone according to Equa-
tion 2.
OEt
P* O
OEt
P* O
ZnCl2
acetone
Mes
Mes
ZnCl2
(2)
NH
tBu
N*
tBu
H
3, 95%
2
After the slow evaporation of the solvent, some color-
less plate-shaped crystals of compound 3 were obtained.
The washed (iso-hexane) and dried crystalline material of
compound 3 was used for the acquisition of all analytical
data.
Figure 1:ꢀThe displacement ellipsoid (30% probability level) plot
and the numbering scheme of the dimeric structure of compound 2
in the crystal.
C-H hydrogen atoms are omitted. Hydrogen bond distance [Å] and
angle [°]: N(1)-H(1)ꢁ·ꢁ·ꢁ·ꢁO(1A) 3.001(3), 170(3). Symmetry code: (A) 1-x,
1-y, 1-z.
A
31P{1H} NMR spectrum (CDCl3) showed one broad
singlet resonance at δ 54.2 ppm (ν1/2ꢀ=ꢀ78.6 Hz), which
is low field shifted (9.6 ppm) as compared with the
signal of compound 2. The line width of the signal likely
Table 1:ꢀCrystallographic data for compounds 2 and 3.
2
3
Empirical formula
C16H28NO2P
C16H28Cl2NO2PZn
Formula mass [gꢁ·ꢁmol−1
]
297.36
433.63
T [K]
λ [Å]
Crystal system
Space group
a [Å]
173(2)
173(2)
0.71073
Monoclinic
P21/n
1.54178
Monoclinic
P21/c
10.6794 (12)
11.9199 (13)
14.0925 (16)
90
105.742 (12)
90
11.9168 (10)
17.6511(14)
19.9614 (18)
90
102.971 (9)
90
b [Å]
c [Å]
α [°]
β [°]
γ [°]
V [Å3]
Z
1726.7 (3)
4
4091.6 (6)
8
ρcalcd.[gꢁ·ꢁcm−3
]
1.144
1.408
μ [mm−1
F(000)
]
0.161
4.866
648
1808
Crystal size [mm]
θ range [°]
0.220ꢁꢁ·ꢁꢁ0.160ꢁꢁ·ꢁꢁ0.130
2.617–27.499
−13ꢁ≤ꢁhꢁ≤ꢁ13
−15ꢁ≤ꢁkꢁ≤ꢁ15
−17ꢁ≤ꢁlꢁ≤ꢁ18
14583
3888/0.0769
99.9
3888/1/192
0.927
0.160ꢁꢁ·ꢁꢁ0.120ꢁꢁ·ꢁꢁ0.030
3.381–68.981
−14ꢁ≤ꢁhꢁ≤ꢁ13
−20ꢁ≤ꢁkꢁ≤ꢁ21
−19ꢁ≤ꢁlꢁ≤ꢁ24
29972
7611/0.0637
100.0
7611/2/437
1.551
Index ranges
No. of reflections collected
No. of independent reflections/Rint
Completeness of θmax [%]
Data/Restrains/parameters
GoF(F2)
R1(F) [Iꢁ>ꢁ2σ(I)]
0.0614
0.1615
0.253/ꢁ−0.362
0.0635
0.1953
1.561/ꢁ−1.090
wR2(F2) (all data)
Largest difference peak/hole [eÅ−3
]
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ꢁꢀꢀꢀ
M. Lutter et al.: Diorganophosphinic acid ester and its zinc complexꢂ ꢂ3
Figure 2:ꢀThe displacement ellipsoid (30% probability level) plot and the numbering scheme of the dimeric structure of compound 3 in the
crystal.
The C-H hydrogen atoms are omitted. Selected interatomic distances [Å]: Zn(1)-Cl(1) 2.2417(12), Zn(1)-Cl(2) 2.2035(13), Zn(1)-O(1) 2.002(3),
Zn(1)-N(1) 2.113(3), Zn(2)-Cl(3) 2.2346(12), Zn(2)-Cl(4) 2.2033(13), Zn(2)-O(3) 2.017(3), Zn(2)-N(2) 2.105(3). Selected interatomic angles
[°]: Cl(1)-Zn(1)-Cl(2) 116.95(5), Cl(1)-Zn(1)-N(1) 107.64(11), Cl(1)-Zn(1)-O(1) 107.50(10), Cl(2)-Zn(1)-N(1) 121.71(11), Cl(2)-Zn(1)-O(1) 111.14(10),
N(1)-Zn(1)-O(1) 87.44(13), Cl(3)-Zn(2)-Cl(4) 116.18(5), Cl(3)-Zn(2)-N(2) 110.34(11), Cl(3)-Zn(2)-O(3) 110.42(10), Cl(4)-Zn(2)-N(2) 119.88(11),
Cl(4)-Zn(2)-O(3) 108.44(11), N(2)-Zn(2)-O(3) 87.66(14). Hydrogen bond distances [Å] and angles [°]: N(1)-H(1)ꢁ·ꢁ·ꢁ·ꢁCl3 3.502(4), 173(6);
N(2)-H(2)ꢁ·ꢁ·ꢁ·ꢁCl1 3.470(4), 171(5).
indicates the kinetic lability of the complex 3 in solution ranging between 121.71(11)° (Cl2-Zn1-N1) and 87.44(13)°
and an equilibrium 2ꢀ+ꢀZnCl2ꢀꢀ3, which is on the onset (N1-Zn1-O1).
of becoming slow on the NMR time scale. Alternatively,
The graph set analysis of compound 3 gives two finite
an epimerization induced by the rupture of either the patterns on the unitary elemental level (N1ꢀ=ꢀDD). The
P=O→Zn or N→Zn coordination could also account for pattern on the binary elemental level is an eight-membered
2
the broadening of the 31P NMR resonance. However, this ring and can be described with
Consider-
N2 (a,b) = R2 (8).
1
was not investigated in further detail. A H NMR spec- ing this eight-membered ring, the Cl(2) and Cl(4) atoms
trum showed an ABX pattern for the PCH2N methylene are trans, as are the five-membered Zn(1)-N(1)-C(10)-P(1)-
protons at δ 3.13/3.39 ppm (JABꢀ=ꢀ14.8 Hz, JAXꢀ=ꢀ9.5 Hz, O(1) and Zn(2)-N(2)-C(60)-P(2)-O(2) chelate rings.
JBXꢀ=ꢀ6.4 Hz).
An ESI mass spectrum (positive mode) showed four
mass peaks at m/zꢀ=ꢀ320.17, 298.19, 213.10, and 185.07, which
+
+
are assigned to the cationic species [2ꢀ+ꢀNa] , [2ꢀ+ꢀH] , Conclusion
+
+
[MesPH(O)(OEt)ꢀ+ꢀH] , and [MesP(OH)2ꢀ+ꢀH] , respectively.
The absence of the mass peak of the zinc complex 3 indi- When coordinated with the zinc dichloride, the nitrogen
cates that a positively charged zinc complex is not stable atom of tert-butylaminomethyl(mesityl)phosphinic acid
under the experimental ESI MS conditions employed.
ethyl ester 2 is a stereogenic center, in addition to the one
From its solution in acetone, compound 3 precipitated at the phosphorus atom. This means that two diastereom-
as colorless plate-shaped crystals. The compound crys- ers are possible for the resulting zinc dichloride complex
tallized in the monoclinic space group P21/c with eight 3. However, apparently, the complexation proceeds dias-
molecules in the asymmetric unit (Figure 2). The hydrogen tereoselectively. Only one diastereomer was observed in
bond distances and angles are given in the figure caption. the solid state. Although this has been established only
Crystallographic data are given in Table 1.
for the single crystal actually measured, it is rather likely
The Zn(1) and Zn(2) atoms are four-coordinated by to hold also for the bulk material. The diastereomer with
Cl(1), Cl(2), O(1) and N(1), and Cl(3), Cl(4), O(3) and N(2), the tert-butyl substituents in cis-position should be less
respectively, at distances of 2.2417(12), 2.2035(13), 2.002(3), favored. This phenomenon needs to be evaluated by
and 2.113(3) Å, respectively, and 2.2346(12), 2.2033(13), further experiments as well as DFT calculations. Nev-
2.017(3) and 2.105(3) Å, respectively. The Cl(1) and Cl(3) ertheless, the results demonstrate, to some extent, the
atoms are involved in the hydrogen bonds (N1-H1ꢀ·ꢀ·ꢀ·ꢀCl3 high potential the title compound and related derivatives
3.502(4), N2-H2ꢀ·ꢀ·ꢀ·ꢀCl1 3.469(4) Å). Consequently, the Zn(1)- hold for such stereoselective reactions. In addition, the
Cl(1) and Zn(2)-Cl(3) distances are slightly longer than N-H function in both the ester 2 and the zinc dichloride
the Zn(2)-Cl(2) and Zn(2)-Cl(4) distances. The zinc atom complex 3 is involved in the hydrogen bridges and creates
exhibits a distorted tetrahedral environment with angles supramolecular structures.
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ꢀꢀꢀꢁ
4ꢀ ꢀM. Lutter et al.: Diorganophosphinic acid ester and its zinc complex
100.0 mmol) was heated (65°C) for 96 h under pressure. The result-
ing solid was filtered, washed with cold iso-hexane, dried and identi-
fied as tert-butylammoninium iodide by means of the melting point
(220°C). The volatiles of the filtrate were removed under reduced pres-
sure. The residue was dissolved in dichloromethane (10 mL), acidi-
fied with diluted hydrochloric acid (10 mL, 1 m), and extracted with
water (3ꢀ×ꢀ10 mL). The combined aqueous phases were treated with
a diluted sodium hydroxide solution (1 m) to pH >10 and extracted
with dichloromethane (3ꢀ×ꢀ10 mL). After drying the combined organic
phases over magnesium sulphate and performing filtration, the vola-
tiles of the resulting solution were removed under reduced pressure.
Compound 2 (1.930 g, 6.5 mmol, 65%) was obtained as a colorless
block-shaped crystalline solid with a melting point of 67°C.
Experimental
Crystallography
Intensity data for compound 2 were collected on an XcaliburS CCD
diffractometer (Oxford Diffraction, Oxford, England) using Mo-Kα
radiation at 173(1) K with an Oxford Cryostream. The intensity data
for compound 3 were collected on an APEX-II CCD diffractometer
(Bruker Corporation, Billerica, MA, USA) using Cu-Kα radiation at
100 K.
The structures were solved with direct methods using
SHELXS-97 (compound 2) or SHELXS-2014/7 (compound 3) (Shel-
drick, 2008, 2015) and refinements were carried out against F2 by
using SHELXL-2014/7 (Sheldrick, 2008, 2015). The C-H hydrogen
atoms were positioned with idealized geometry and refined using a
riding model. All non-hydrogen atoms were refined using anisotropic
displacement parameters. The NH protons of all compounds were
located in the difference Fourier map and refined freely; the N-H dis-
tances were restrained to a fix value.
CCDC-1831583 (2) and CCDC-1831584 (3) contain the supplemen-
tary crystallographic data for this paper. This data can be obtained
free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. For the decimal rounding of
numerical parameters and su values, the rules of IUCr have been
employed (Clegg, 2003). All Figures were generated using ORTEP
III (Farrugia, 1997; Farrugia, 2012) visualization software. The graph
sets were calculated using cthe alculation routine of Mercury (Mac-
rae et al., 2006, 2008).
4
1H NMR: (300.13 MHz, CDCl3, 298 K, 16 scans): δ 6.76 (d, J(1H-
31P)ꢀ=ꢀ3.7 Hz, 2H, CmH), 4.15–4.02 (complex pattern, 1H, CH2CH3),
3.89–3.76 (complex pattern, 1H, CH2CH3), 3.02-2.85 (complex pat-
tern, 2H, PCH2N), 2.51 (s, 6H, CoCH3), 2.14 (s, 3H, CpCH3), 1.20 (t,
1
3J(1H- H)ꢀ=ꢀ7.1 Hz, 3H, CH2CH3), 0.89 (s, 9H, C(CH3)3). 13C{1H} NMR:
(75.48 MHz, CDCl3, 298 K, 640 scans): δ 143.1 (d, J(13C- P)ꢀ=ꢀ11.2 Hz,
2
31
4
31
3
31
Co), 141.2 (d, J(13C- P)ꢀ=ꢀ2.8 Hz, Cp), 130.3 (d, J(13C- P)ꢀ=ꢀ12.7 Hz, Cm),
123.6 (d, J(13C- P)ꢀ=ꢀ120.4 Hz, Ci), 60.0 (d, J(13C- P)ꢀ=ꢀ6.5 Hz, CH2CH3),
1
31
2
31
50.3 (d, 3J(13C- P)ꢀ=ꢀ14.6 Hz, C(CH3)3), 43.0 (d, 1J(13C- P)ꢀ=ꢀ110.1 Hz,
31
31
PCH2N), 28.1 (s, C(CH3)3), 22.9 (d, 3J(13C- P)ꢀ=ꢀ2.3 Hz, ortho-CoCH3), 20.6
31
(d, 5J(13C- P)ꢀ=ꢀ0.9 Hz, para-CpCH3), 16.1 (d, 3J(13C- P)ꢀ=ꢀ6.4 Hz, CH2CH3).
31
31
31P{1H} NMR: (121.50 MHz, CDCl3, 298 K, 128 scans): δꢀ=ꢀ44.6 (s, 1J(31P-
13C)ꢀ=ꢀ120.3 Hz, J(31P- C)ꢀ=ꢀ110.1 Hz). Elemental analysis: calculated
1
13
(found) for C16H28NO2P 64.6 (64.8)% C, 9.5 (9.3)% H, 4.7 (4.7)% N. ESI
+
+
MS: (acetonitrile, m/z, positive mode): 617.3 [2 2ꢀ+ꢀNa] , 320.1 [2ꢀ+ꢀNa] ,
298.1 [2ꢀ+ꢀH] . IR: (cm−1): νN-H 3288, νP=O 1212.
+
General
N-(tert-butyl)aminomethyl(mesityl)phosphinic acid ethyl
ester zinc chloride complex (3)
Solvents, including NMR solvents, were purified by distillation from
the appropriate drying agents under argon and stored over molecu-
lar sieves. The NMR spectra were recorded at room temperature on
a Bruker AV DPX 300. NMR chemical shifts were given in ppm and
were referenced to Me4Si (1H, 13C) (using residual solvent signal: CDCl3
1H 7.27 ppm, 13C 77.0 ppm) and H3PO4 (85%, 31P). Elemental analyses
were performed on a LECO-CHNS-932 analyzer (LECO Corporation,
St. Joseph, MI, USA). The samples were weighted at air. The uncor-
rected melting points were measured on a Büchi M-560 (Büchi
Labortechnik GmbH, Essen, Germany). The electrospray mass spectra
were recorded with a Thermoquest-Finnigan instrument (Scientific
Instrument Services, Ringoes, NJ, USA). The concentration was 0.1 mg/
mL with a flow rate of 10 μL/min. The experimental isotopic pattern
matched the theoretical ones. IR spectra (cm−1) were measured on a
Perkin Elmer Spectrum Two (ATR, PerkinElmer, Inc., Waltham, MA,
USA). The synthesis of compound 1 has already been published. (Lutter
and Jurkschat, 2018). The tert-butyl amine (98%) was purchased (abcr
GmbH, Karlsruhe, Germany). The latter was dried (CaH2) and distilled
prior before use. The zinc chloride (97%) was purchased (abcr GmbH,
Karlsruhe, Germany) and used without further purification.
To a solution of the secondary amine 2 (0.120 g, 0.4 mmol) in acetone
(5 mL) zinc chloride (0.550 g, 0.4 mmol) was added. After the slow
evaporation of the solvent, the complex 3 was obtained as a colorless
plate-shaped crystalline solid (0.164 g, 0.38 mmol, 95%) with a melt-
ing point of 180°C (decomposition).
4
1H NMR: (300.13 MHz, CDCl3, 297 K, 16 scans): δ 6.97 (d, J(1H-
31P)ꢀ=ꢀ4.5 Hz, 2H, CmH), 4.34–3.97 (complex pattern, 2H, CH2CH3),
2
1
2
3.39 (ABX pattern, J(1H- H)ꢀ=ꢀ14.8 Hz, J(1H-31P)ꢀ=ꢀ9.5 Hz, 1H, PCH2N),
2
1
2
3.13 (ABX pattern, J(1H- H)ꢀ=ꢀ14.8 Hz, J(1H-31P)ꢀ=ꢀ6.4 Hz, 1H, PCH2N),
2.59 (d, 4J(1H-31P)ꢀ=ꢀ1.2 Hz, 6H, CoCH3), 2.32 (s, 3H, CpCH3), 1.38 (s,
9H, C(CH3)3), 1.36 (t, 3J(1H- H)ꢀ=ꢀ7.1 Hz, 3H, CH2CH3). 13C{1H} NMR:
1
(75.47 MHz, CDCl3, 297 K, 640 scans): δ 144.7 (d, J(13C-31P)ꢀ=ꢀ2.8 Hz,
4
Cp), 144.1 (d, 2J(13C-31P)ꢀ=ꢀ12.7 Hz, Co), 131.5 (d, 3J(13C-31P)ꢀ=ꢀ14.1 Hz, Cm),
118.5 (d, 1J(13C-31P)ꢀ=ꢀ131.4 Hz, Ci), 63.6 (d, 2J(13C-31P)ꢀ=ꢀ6.7 Hz, CH2CH3),
56.5 (d, 3J(13C-31P)ꢀ=ꢀ9.9 Hz, C(CH3)3), 42.0 (d, 1J(13C-31P)ꢀ=ꢀ102.2 Hz,
PCH2N), 27.9 (s, C(CH3)3), 23.3 (d, J(13C-31P)ꢀ=ꢀ3.0 Hz, CCoH3), 21.2 (d,
3
5J(13C-31P)ꢀ=ꢀ0.8 Hz, CpCH3), 16.1 (d, 3J(13C-31P)ꢀ=ꢀ6.7 Hz, CH2CH3). 31P{1H}
NMR: (121.50 MHz, CDCl3, 297 K, 128 scans): δꢀ=ꢀ54.2 (s, ν1/2ꢀ=ꢀ78.6 Hz).
Elemental analysis: calculated (material from 1st synthesis found,
material from 2nd synthesis found) for C16H28Cl2NO2PZn 44.3 (43.2,
43.5)% C, 6.5 (6.5, 6.5)% H, 3.2 (3.1, 3.1)% N. ESI MS: (material
from 2nd synthesis, acetonitrileꢀ+ꢀwater 1:1ꢀ+ꢀ0.1% trifluoro acetic
N-(tert-butyl)aminomethyl(mesityl)phosphinic acid
ethyl ester (2)
+
+
acid, m/z, positive mode): 320.17 [2ꢀ+ꢀNa] , 298.19 [2ꢀ+ꢀH] , 213.10
+
+
[MesPH(O)(OEt)ꢀ+ꢀH] , 185.07 [MesP(OH)2ꢀ+ꢀH] . ESI MS: (material
A stirring solution of iodomethylmesitylphosphinic acid ethylester from 2nd synthesis, acetonitrile, m/z, positive mode): 595.38 [2
(1) (3.520 g, 10.0 mmol) in freshly distilled tert-butyl amine (10.5 mL, 2ꢀ+ꢀH] , 298.19 [2ꢀ+ꢀH] . IR: (cm−1): νN-H 3197, νP=O 1150.
+
+
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ꢁꢀꢀꢀ
M. Lutter et al.: Diorganophosphinic acid ester and its zinc complexꢂ ꢂ5
Kaboudin, B.; Haghighat, H.; Yokomatsu, T. A novel method for
the separation of bis(alpha-hydroxyalkyl)phosphinic acid
diastereoisomers via formation of novel cyclic phosphinic
acids. J. Org. Chem. 2006, 71, 6604–6606.
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