Facile phosphite to phosphonate rearrangement of a trialkanolamine-derived triphosphite promoted by triethylaluminum

Article abstract of DOI:10.1080/10426500701513248

A facile room temperature rearrangement of a trialkanolamine-derived triphosphite, 1, to the monophosphonate 5 promoted by three equivalents of triethylaluminum is described. The diphosphonate 6 was prepared by the addition of three equivalents of triethylaluminum to the monophosphonate 5. A mechanism is suggested involving a transition state or intermediate with coordination of the trialkylaluminum to the migrating oxygen. Copyright Taylor & Francis Group, LLC.

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Facile Phosphite to
Phosphonate Rearrangement
of a Trialkanolamine-derived
Triphosphite Promoted by
Triethylaluminum
Sai P. Shum a , Roswell E. King III a , Christopher
Kuell a , Ronald K. Rodebaugh a , Anthony D. DeBellis
a & Stephen D. Pastor a
a Ciba Specialty Chemicals Corporation , Tarrytown,
New York, USA
Published online: 25 Sep 2007.
To cite this article: Sai P. Shum , Roswell E. King III , Christopher Kuell , Ronald K.
Rodebaugh , Anthony D. DeBellis & Stephen D. Pastor (2007) Facile Phosphite to
Phosphonate Rearrangement of a Trialkanolamine-derived Triphosphite Promoted by
Triethylaluminum , Phosphorus, Sulfur, and Silicon and the Related Elements, 182:11,
2611-2623, DOI: 10.1080/10426500701513248
To link to this article: http://dx.doi.org/10.1080/10426500701513248
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Phosphorus, Sulfur, and Silicon, 182:2611–2623, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701513248
Facile Phosphite to Phosphonate Rearrangement
of a Trialkanolamine-derived Triphosphite Promoted
by Triethylaluminum1
Sai P. Shum
Roswell E. King III
Christopher Kuell
Ronald K. Rodebaugh
Anthony D. DeBellis
Stephen D. Pastor
Ciba Specialty Chemicals Corporation, Tarrytown, New York, USA
A facile room temperature rearrangement of a trialkanolamine-derived triphos-
phite, 1, to the monophosphonate 5 promoted by three equivalents of triethylalu-
minum is described. The diphosphonate 6 was prepared by the addition of three
equivalents of triethylaluminum to the monophosphonate 5. A mechanism is sug-
gested involving a transition state or intermediate with coordination of the trialky-
laluminum to the migrating oxygen.
Keywords Aluminum-phosphorus interaction; Michaelis-Arbusov reaction; P C bond
formation; phosphonate; Phosphite Rearrangement; trialkylaluminum; triethylalu-
minum
INTRODUCTION
The coordination of phosphites to late transition metals is well known
in the literature. The use of both achiral and chiral phosphite ligands
have been reported as viable alternatives to phosphine ligands in tran-
sition metal complexes.2−9 Recently, we communicated the synthesis,
solid-state conformation, and utility of a sterically congested achiral
triethanolamine-derived trisphosphite 1 and the corresponding chiral
tri-2-propanolamine phosphite ligand (S, S, S)-2 (Figure 1) in the Rh(I)-
catalyzed asymmetric hydrosilation of ketones.10,11
Received November 7, 2006; accepted May 4, 2007.
The authors wish to thank Ciba Specialty Chemicals Corp. for support and permission
to publish this work. The authors thank Mrs. L. Burke for acquiring NMR spectral data;
Mr. B. Piatek for MS; and Mr. M. Nirsberger for obtaining IR spectra.
Address correspondence to Sai P. Shum, Ciba Specialty Chemicals Corporation, 540
White Plains Road, Tarrytown, New York 10591, USA. E-mail: sai.shum@cibasc.com
2611

2612
S. P. Shum et al.
FIGURE 1 The Chem. Abstr. numbering system for the dibenzo[d,f][1,3,2]
dioxaphosphepin ring system.
In contrast to the numerous studies on the formation and use of
transition-metal complexes of phosphites, the interaction of phosphites
with aluminum has received scant attention in the literature.12,13 In a
recent monograph on 31P NMR spectroscopy, a few reports of 27Al – 31
P
one-bond couplings (240–290 Hz) were cited.14 The paucity of studies
is surprising because phosphites are known to be processing stabilizers
for polyolefins, where low levels of residual aluminum may be present
from the polymerization catalysts.15 Methylalumoxane , for example,
is a well known co-catalyst in Ziegler-Nata type polymerizations of
olefins. However, catalysts for both polymerization and oligomerization
are often complex mixtures that may include triakylaluminum com-
pounds in which the exact structure of the catalyst is unknown.15e The
sterically congested triethanolamine phosphite 1 has been suggested
to be a particularly effective processing stabilizer for polyolefins, in
which peroxide decomposition was suggested to be the major stabiliza-
tion mechanism.16 The rearrangement of a phosphite to phosphonate
by tributylaluminum reported by Sander17 suggests that other mech-
anisms besides peroxide decomposition by phosphites may be involved
in polymer stabilization. We report herein a study on the interaction of
triethylaluminum with the triethanolamine phosphite 1.
RESULTS AND DISCUSSION
Synthesis
The biphenyl-2,2ꢀ-diol 3 was prepared by the oxidative coupling of 2,4-
di-tert-butylphenol with hydrogen peroxide under alkaline conditions
as previously described by Shum et al.18 The phosphorochloridite 4 was
prepared in situ by the reaction of 3 with phosphorus(III) chloride in
the presence of triethylamine as an acid acceptor (Scheme 1).19,20 The

Phosphite to Phosphonate Rearrangement
2613
SCHEME 1

2614
S. P. Shum et al.
reaction of three equivalents of 4 with an equivalent of triethanolamine
in the presence of triethylamine gave the tripodal phosphite 1 as de-
scribed previously by Shum et al.11 A cross peak is observed in the
15
indirect detection { N/1H} gHMBC 2D NMR (CDCl3)(50.59 MHz) ex-
periment on 1 indicating a nitrogen chemical shift at δ − 356.8, which
is in the region expected for a tertiary amine nitrogen. The associated
proton resonance evidences a three-bond correlation between the nitro-
gen atom and the methylene hydrogens of the carbon atom bonded to
oxygen.
Interaction with Aluminum(III)
1
In the 31P{ H} NMR(CD2Cl2) spectrum of 1 at 26◦C, a single sig-
nal is observed at δ 140.6 due to conformational averaging.21 In the
1
31P{ H} NMR spectrum of the product formed by the reaction of 1
with three equivalents of triethylaluminum at ambient temperature
(dichloromethane-d2 with strict exclusion of oxygen and moisture), two
singlets are observed at δ 138.4 and δ 35.4 in a 2:1 ratio by integration of
their respective peak areas. No other signals due to phosphorus contain-
1
ing species were observed in the 31P{ H} NMR spectrum immediately
after the addition of the trialkylaluminum (Scheme 2). Upon further ad-
dition of 1 to the reaction mixture, an additional singlet at δ 139.3 was
observed that was assigned to 1, which demonstrates that the singlet
at δ 138.4 is due to the presence of a new compound. A early communi-
cation suggested that these observations were due to the complexation
of Al(III) with the nitrogen and one phosphorus atom of 1.1 However,
preliminary molecular orbital calculations on a number of conforma-
tions of a model six-membered chelate, in which both a nitrogen and
phosphorus atom were coordinated to trimethylaluminum (used as a
model), suggested that such a complex was not stable with respect to
the dissociation of the phosphorus atom from aluminum.22 Previously,
Sander reported that tributylaluminum formed a coordination complex
with tributyl phosphite that underwent a Michaelis-Arbusov-type re-
action to the phosphonate when heated to 80◦C.17 The oxygen of the
resultant phosphonate was strongly coordinated to Al(III), and the free
phosphonate was obtained by hydrolysis or alcoholysis.17,23 Nykerk23
reported that the dissociation enthalpy of an adduct of AlMe3 with
trimethylphosphate is 25.6 kcal·mol−1. The reaction of tributyl phos-
phite with trimethylaluminum was shown to be a stoichiometric rather
than catalytic reaction.17
Indeed, scaling up the reaction of 1 with three equivalents of tri-
ethylaluminum led to the isolation of the monophosphonate 5.24 In the
1H NMR spectrum of 5, a doublet of triplets at δ 2.08(2JHCP = 18.7 Hz;

Phosphite to Phosphonate Rearrangement
2615
SCHEME 2
3JHCCH = 8 Hz) is observed, which was assigned to the methylene pro-
tons of the carbon atom bonded to the P(V) atom. The magnitude of
2
the observed JHCP coupling as well as the chemical shift observed
is consistent with a molecule containing a methylene carbon atom
bonded to phosphorus.25 A doublet of triplets was observed at δ 2.91
(3JHCCP = 6.2 Hz; 3JHCCH = 8 Hz), which was assigned to the methylene
protons beta to the P(V) atom. In the 1H-31P heteronuclear generalized
HMBC (1H-detected multiple-bond heteronuclear multiple-quantum
coherence)26 spectrum of 5, cross peaks between the P(V) singlet at δ
33.9 with the proton signals at δ 2.08 and δ 2.91 clearly established the
connectivity. Consistent with this interpretation, cross peaks between
the P(III) atom at δ 138.4 with the proton signal at δ 3.75 (3JHCOP = 8 Hz;
3JHCCH = 6.5 Hz) and δ 2.61 (3JHCCH = 6.5 Hz) are observed. Small dif-
1
ferences between the 31P{ H} chemical shifts in the NMR spectrum

2616
S. P. Shum et al.
of the P phosphorus atoms in 5 in the reaction mixture and isolated
product are suggested to be due to the complexation of the product
phosphonate 5 oxygen atom as well as the nitrogen atom of 5 with
aluminum in the crude reaction mixture, which alters the electronic
1
environment about the phosphorus atoms. In the 13C{ H} NMR spec-
trum of 5, a doublet is observed at δ 24.24 (1JPC = 130.9 Hz) that was
assigned to a methylene carbon atom bonded to phosphorus. The mag-
nitude of the one-bond J coupling constant is completely consistent with
a carbon atom bonded to phosphorus.11 Cross peaks are observed in the
15
indirect detection { N1H} gHMBC 2D NMR (CDCl3) experiment on 5
indicating a nitrogen chemical shift at δ –351.2, as expected for a ter-
tiary amine nitrogen. The cross peaks evidence three bond interactions
between the nitrogen atom and the methylene protons on carbon alpha
to phosphorus and the methylene protons on carbon alpha to oxygen.
The complexation of both the phosphonate oxygen and nitrogen in 5,
as well as the complexation of the nitrogen in 1, with aluminum pro-
vides a possible explanation for the observation that three equivalents
of triethylaluminum is required for facile rearrangement of 1 to the
monophosphonate 5, albiet, if this is the case, the stoichiometry of the
reaction suggests that only two equivalents of triethylaluminum is re-
quired. However, the aggregation state of the aluminum in the reaction
medium is unknown and may not be monomeric, which is a possible ex-
planation of the observed stochiometry. No evidence for the formation
of the diphosphonate 6 was observed in the crude reaction mixture, vide
infra. If the mechanism of the observed rearrangement of the phosphite
1 to the phosphonate 5 is similar to that of a traditional Michaelis-
Arbusov rearrangement27 of a trialkylphosphite where Al(III) is acting
as a Lewis acid (see Figure 2), a triaryl phosphite would not be expected
to undergo a facile ambient-temperature rearrangement with triethyla-
luminum. Triphenyl phosphite, for example, only undergoes rearrange-
ment with alkyl iodides at 200◦C.27b The addition of triethylaluminum
to a solution of the triaryl phosphite 7 (Scheme 3) showed no evidence
SCHEME 3

Phosphite to Phosphonate Rearrangement
2617
FIGURE 2 Mechanism of a typical Michaelis-Arbusov-type reaction involving
a phosphite and a hydrogen halide.
1
for reaction in the 31P{ H} NMR spectrum of the reaction mixture at
ambient temperature. These observations are also consistent with the
rearrangement of the alkyl-oxygen bond rather than the aryl-oxygen
bond in phosphite 1. The observed phosphite to phosphonate rearrange-
ment of 1 to 5 with triethylaluminum does not involve the loss of any
substituents and the mechanism would appear to be somewhat dif-
ferent that the typical mechanism proposed for the Michaelis-Arbusov
reaction, although both organotin halides28 and cyanogen iodide29 are
known to promote the reaction. Previous uncatalyzed thermal isomer-
izations of phosphites to phosphonates has been attributed to the pres-
ence of trace impurities, although the photochemical rearrangement
of low molecular weight phosphites is well documented.30 A transition
state or intermediate involving coordination of aluminum to oxygen
leading to either an ion pair or concerted rearrangement may be in-
volved as illustrated in Figure 3. The possible involvement of the ni-
trogen atom beta to the migrating oxygen remains speculative. The
involvement of the alkyl-oxygen bond in the suggested transition state
or intermediate in the rearrangement of phosphite 1 to phosphonate 5 is
consistent with the unreactive nature of the aryl-oxygen bonds present
in 1 (higher bond strength of a Csp2 O compared to a Csp3 O bond).
The spectral data on the product of the reaction of 5 with three equiv-
alents of triethylaluminum was fully consistent with the diphosphonate
6. No evidence for the formation of the trisphosphonate was observed
1
in the 31P{ H} NMR spectrum of the crude reaction mixture. In the

2618
S. P. Shum et al.
FIGURE 3 Suggested transition state or intermediate for the triethylalu-
minum promoted rearrangement of a phosphite 1 to the phosphonate 5 with
the phosphoryl oxygen coordinated to aluminum.
1
31P{ H} NMR spectrum of 6, two singlets are observed at δ 135.93 and
δ 33.84 in a 1:2 ratio by integration of their respective peak areas. The
1
integration of the proton signals in the H NMR spectrum of 6 is that
expected for the diphosphonate structure illustrated.
CONCLUSIONS
The interaction of triethylaluminum with the trialkanolamine phos-
phite 1 was shown to lead to a facile phosphite to phosphonate re-
arrangement at room temperature. A mechanism is suggested that
involves prior coordination of the aluminum alkyl to oxygen in the
transition state or intermediate. A prior limited study on the trimethy-
laluminum promoted rearrangement of a trialkyl phosphite to a
phosphonate reported that elevated temperatures are required for the

Phosphite to Phosphonate Rearrangement
2619
reaction to proceed. The reason for the occurrence of a facile room tem-
perature phosphite to phosphonate rearrangement of 1 to 5 with tri-
ethylaluminum suggests further mechanistic studies are warranted.
Furthermore, the rearrangement of a phosphite to phosphonate by
residual catalytic aluminum species in a polymer matrix during high-
temperature processing may be an unrecognized mechanism of polymer
stabilization.32
EXPERIMENTAL
All melting points were determined in open capillary tubes with a
Thomas-Hoover melting point apparatus and are uncorrected. 1H NMR
(300.08 MHz and 499.84 MHz, respectively) spectra were obtained on a
Varian Model Gemini-300, Unity-500, or Unity-INOVA 500 spectrome-
ters. 13C NMR (125.70 MHz) spectra and 15N NMR (50.59 MHz) spectra
were obtained on a Varian Model Unity-INOVA 500. 31P NMR (202.33
and 121.47 MHz, respectively) spectra were obtained on a Varian Model
Unity-500, Unity-INOVA 500, or Gemini-300 spectrometers. All 31Pand
1
31P{ H} chemical shift values (proton coupled and decoupled, respec-
tively) are reported in ppm relative to 85% phosphoric acid (external),
where a positive sign is downfield from the standard. 15N chemical shift
values are reported in ppm relative to nitromethane, where a positive
sign if downfield from the standard.31 Significant 1H NMR spectral
data are tabulated in the following order: multiplicity (m, multiplet;
s, singlet; d, doublet; t, triplet; dd, doublet of doublets; dq, doublet of
quartets; dt, doublet of triplets; ddt, doublet of doublets of triplets),
atom assignments, coupling constant in Hertz, and number of pro-
tons. IR spectra were obtained on a Bruker model Vector 22. Merck
silica gel 60 (200–400 mesh) was used for column chromatography. MS
spectra obtained on a Perspective Biosystems Voyager DE-STR ma-
trix assisted laser desorption ionization mass spectrometer (MALDI
TOF) equipped with a 337 nm N2 laser and a time of flight analyzer.
The instrument was operated in the positive ion reflector mode with
an accelerating voltage of 24,900 volts. The samples were prepared by
depositing a methylene chloride solution of the substrate onto a gold-
metal coated sample plate. 2-Benzotriazol-2-yl-4-methyl-phenol was de-
posited as a matrix and silver trifluoroacetate (11 mg.mL−1 acetonitrile)
was used as a cationization agent. Mass spectra were also obtained on
a Fison VG Platform II mass spectrometer in APcI positive scanning
mode. Merck pre-coated (0.25 mm) silica gel F-254 plates were used
for TLC. Reagents were purchased from commercial laboratory sup-
ply houses. Tris(2,4-di-tert-butylphenyl) phosphite, 7, is commercially
available from Ciba Specialty Chemicals Corporation. Toluene and

2620
S. P. Shum et al.
triethanolamine were dried over 4 Angstrom molecular sieves prior to
use. Reactions were carried out in flame-dried apparatus under a dry in-
ert atmosphere of either nitrogen. Elemental analyses were performed
by the Analytical Research Department, Ciba Specialty Chemicals.
Reaction Product of 1 with Triethylaluminum, (5)
To a solution of 1 (4.38 g, 3 mmol) in 50 mL of dichloromethane was
added dropwise a 1M solution of triethylaluminum (9 mL, 9 mmol)
in hexane. The reaction mixture was stirred for 2 h at ambient tem-
perature until no starting material was observed by 31P NMR. The
reaction solvent and volatiles were removed in vacuo. The residue
was purified by dry-column chromatography (95:5 heptane: ethyl ac-
etate eluent) followed by trituration with acetonitrile to give 1.14 g
(26%) of a white solid, mp 149–152◦C. IR(neat sample-Attenuated To-
1
tal Reflectance) v 1228 cm−1 (P O); 15N{ H} NMR(CDCl3)(50.59 MHz)
1
δ − 351.2; 31P{ H} NMR(CD2Cl2)(202.36 MHz) δ 138.4 (s, 2P ), 35.4 (s,
1
1P ); H NMR(CD2Cl2)(499.85 MHz) δ 1.33 (s, 36 H), 1.34 (s, 18 H),
1.40 (s, 36 H), 1.41 (s, 18 H), 2.08 (dt, CH P( O),2JHCP = 18.7 Hz,
JHCCH = 8.0 Hz, 2 H), 2.61 (t, CH N, 3JHCCH2= 6.5 Hz, 4 H), 2.91 (dt,
3
2
CH N, 3JHCCP = 6.2; 3JHCCH = 8.0 Hz, 2 H), 3.75 (dt, CH OP, 3JHCCH
=
2
2
3
4
6.5 Hz, JHCOP = 8.0 Hz, 4 H), 7.14 (d, JHCCCH = 2.4 Hz, 4 H), 7.17
(d, 4JHCCCH = 2.4 Hz, 2 H), 7.41 (d, 4JHCCCH = 2.4 Hz, 4 H), 7.47 (unre-
1
solved dd, 4JHCCCH =2.4 Hz, 2 H); 13C{ H} NMR (CD2CL2) (75.46 MHz)
δ 24.2 (d, CP O, 1JCP = 130.9 Hz), 31.0 (d, CCH3, 5JCP = 2.7 Hz), 31.2
(s, CCH3), 31.3 (s, CCH3), 31.4 (s, CCH3), 34.7 (s, CCH3), 34.8 (s, CCH3),
35.4 (s, CCH3), 35.5 (s, CCH3), 48.8 (s, CCH2P), 54.5 (d, CCH2OP,
3JCCOP = 3.1 Hz), 62.8 (d, CH2OP, 2JCOP = 5.3), 124.4 (s), 125.4 (s), 126.5
(s), 127.1 (s), 130.6 (s), 132.7 (d, 3JPC = 3.7 Hz ), 140.0 (d, 3JPC = 4.1 Hz),
2
3
140.1 (s), 144.4 (d, JPC = 10.1 Hz), 146.0 (d, JPC = 5.7 Hz), 146.8 (s),
147.9 (s). MS(LC/APcI+) [M+1]1464; Anal. Calcd. for C90H132NO9P3:
C, 73.79; H, 9.08; N, 0.96. Found: C, 73.73; H, 9.12; N, 0.82.
Reaction Product of 5 with Triethylaluminum, (6)
To a solution of 1 (0.6 g, 0.4 mmol) in 10 mL of dichloromethane was
added dropwise a 1M solution of triethylaluminum (1.2 mL, 1.2 mmol)
in hexane. The reaction mixture was stirred for 1 h at ambient tempera-
ture until no starting material was observed by 31P NMR. The reaction
solvent and volatiles were removed in vacuo. The residue was purified
by dry-column chromatography (90:10, heptane: ethyl acetate eluent)
followed by trituration with acetonitrile to give 0.14 g (24%) of a white
1
solid, m.p. 181–185◦C. 31P{ H} NMR(CDCl3)(121.48 MHz) δ 135.93 (s,

Phosphite to Phosphonate Rearrangement
2621
1
1P), 33.84 (s, 2P); H NMR(CDCl3)(300.08 MHz) δ 1.28 (s, 18 H), 1.35
(s, 36 H), 1.41 (s, 18 H), 1.44 (s, 36 H), 2.14 (dt, CH P( O),2JHCP
=
2
3
18.7 Hz, JHCCH = 8.0 Hz, 4 H), 2.56 (t, CH2N, 3JHCCH = 6.5 Hz, 2 H),
3
3
2.95 (dt, CH2N, JHCCP = 6.2; JHCCH = 8.0 Hz, 4 H), 3.74 (dt, CH2OP,
3JHCCH = 6.5 Hz, 3JHCOP = 8.0 Hz, 2 H), 7.16 (d, 4JHCCCH = 2.4 Hz, 4 H),
4
4
7.17 (d, JHCCCH = 2.4 Hz, 2 H), 7.40 (d, JHCCCH = 2.4 Hz, 2 H), 7.48
(unresolved dd, 4JHCCCH = 2.4 Hz, 4 H).
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Rihs, B. Piatek, and R. K. Rodebaugh, Inorg. Chem., 42, 5097 (2003).
[12] For an example of a molecule with phosphorus coordinated to aluminum, see H. H.
Karsch, A. Appelt, F. Ko¨hler, and G. Mu¨ller, Organometallics, 4, 231 (1985).
[13] For a review, see G. H. Robinson, Coordination Chemistry of Aluminum (VCH: New
York, 1993), Chapter 1.
[14] J. G. Verkade and J. A. Mosbo, In Phosphorus-31 NMR Spectroscopy in Stereochem-
ical Analysis: Organic Compounds and Metal Complexes; L. D. Quin, and J. G.
Verkade, Eds. (VCH: Weinheim, 1987); 446.
[15] For reviews and leading references, see (a) D. James, Encyclopedia of Polymer
Science and Engineering, Vol 6 (Wiley-Interscience: New York, 1986); 454; (b)
R. B. Lieberman, Encyclopedia of Polymer Science and Engineering, Vol 13; (Wiley-
Interscience: New York, 1986); p 429; (c) F. Gugumus, Plastics Additives, 3rd ed.;
(Hanser: New York, 1990); Chapter 1; (d) For a review, see A. D. Horton, Trends in
Poly. Sci., 2, 158 (1994); (e) For examples of catalyst systems incorporating trialky-
laluminum co-catalysts, see G. W. Parshall and S. D. Ittel, Homogeneous Catalysis,
2nd ed. (Wiley-Interscience: New York, 1992).
[16] J. D. Spivack, S. D. Pastor, A. Patel, and L. P. Steinhuebel, In Polymer Stabiliza-
tion and Degradation: ACS Symposium Series 280, P. P. Klemchuk, Ed. (American
Chemical Society: Washington, D.C., 1985) 247–257.
[17] M. Sander, Angew. Chem., 73, 67 (1961).
[18] S. P. Shum, S. D. Pastor, and G. Rihs, Inorg. Chem., 41, 127 (2002).
[19] (a) P. A. Odorisio, S. D. Pastor, and J. D. Spivack, Phosphorus Sulfur, 19, 1 (1984);
(b) P. A. Odorisio, S. Pastor, D. J. D. Spivack, D. Bini, and R. K. Rodebaugh, Phos-
phorus Sulfur, 19, 285 (1984).
[20] For the isolation and characterization of 4, see S. D. Pastor, S. P. Shum, R. K.
Rodebaugh, A. D. DeBellis, and F. H. Clarke, Helv. Chim. Acta, 76, 900 (1993).
[21] For a discussion of averaged symmetry, residual stereoisomers, and the NMR of
conformationally mobile systems, see E. L. Eliel, S. H. Wilen, and L. N. Mander,
Stereochemistry of Organic Compounds (Wiley-Interscience: New York, 1994); 54–
58.
[22] A. D. DeBellis, private communication; Calculations were performed using Macro-
Model version 7.0 and Spartan version 5.1 on an SGI Octane or DEC Alphaserver
4000 workstation.
[23] (a) K. M. Nykerk, Inorg. Nucl. Chem. Lett., 4, 253 (1968); (b) The dissociation en-
thalpy of an adduct of AlMe3 with trimethylphosphine oxide is 32 kcal·mole−1, see
C. H. Hendrickson, D. Duffy, and D. P. Eyman, Inorg. Chem., 7, 1047 (1968).
1
[24] The 31P{ H} NMR spectra of the reaction media showed clean conversion of 1 to 5,
with no other phosphorus containing species. The slight chemical shift difference
observed for 5 in the crude reaction mixture suggests that the product was com-
plexed to Al, which is consistent with the observations by Sander (Ref. 17). The Al
that was complexed to 5 in the crude reaction mixture was removed by hydroly-
sis during chromatographic purification. Unfortunately, the ultimate fate of the Al
could not be determined and we suggest it remains on the column after chromato-
graphic purification of the crude reaction mixture. Considerable loss of product on
the column accounts for the low isolated yields, which has been observed previously
for high-molecular-phosphites of this structural class that contain aminic nitrogen.
[25] For 1H NMR spectral data of a phosphonate derivative incorporated in a
dibenzo[d,f][1,3,2]dioxaphosphepin ring, see P. A. Odorisio, S. D. Pastor, and
J. D. Spivack, Phosphorus Sulfur, 20, 273 (1984).

Phosphite to Phosphonate Rearrangement
2623
[26] For an overview of the technique and application examples, see One-dimensional
and Two-dimensional NMR Spectra by Modern Pulse Techniques; K. Nakanishi,
Ed.; (University Science Books: Sausalito, 1990).
[27] (a) For a recent review of the Michaelis-Arbusov reaction, see Quin, L.D. A Guide
to Organophosphorus Chemistry (Wiley-Interscience: New York, 2000); 141–145; (b)
For earlier reviews, see J. Emsley, and D. Hall, The Chemistry of Phosphorus (Harper
and Row: London, 1976); 117–119; (c) R. F. Hudson, Structure and Mechanism
in Organo-phosphorus Chemistry (Academic Press: New York, 1965); 135–140; (d)
R. G. Harvey and E. R. De Sombre, Topics in Phosphorus Chemistry, 1, 57 (1964); (e)
G. M. Kosolapoff, Organophosphorus Compounds (Wiley: New York, 1950); 196–199;
(f) B. A. Arbusov, Organo-Phosphorus Compounds (Butterworths: London, 1964);
307–335.
[28] (a) B. A. Arbuzov and N. P. Grechnik, Zhur. Obshcheˇı Khim, 17, 2166 (1947); (b) B. A.
Arbuzov and A. N. Pudovik, Zhur. Obshcheıˇ Khim., 17, 2158 (1947).
[29] S. Saunders and W. Wild, J. Chem. Soc., 699 (1948).
[30] For a review of variations of the Michaelis-Arbusov reaction, see R. S. Edmundson,
In The Chemistry of Organophosphorus Compounds, Vol. 4, F. R. Hartley, Ed. (Wiley:
Chichester, 1996); 62–69.
[31] See IUPAC recommendation on reporting 15N chemical shift values, Pure Appl.
Chem., 73, 1795 (2001).
[32] Stabilization as a result of chelation of Al to the phosphonate oxygen.