Synthesis and dynamic NMR study of new stable ylides derived from the reaction of triphenylphosphine, dialkyl acetylenedicarboxylates, and 5-ACYL meldrums acid

Article abstract of DOI:10.1080/10426507.2012.668988

Triphenylphosphine and dialkyl acetylenedicarboxylate react smoothly in the presence of 5-acyl Meldrum's acid in dichloromethane at room temperature and lead to synthesis of new stable ylide derivatives of dimethyl (5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dio

Full text of DOI:10.1080/10426507.2012.668988

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Phosphorus, Sulfur, and Silicon and the
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Synthesis and Dynamic NMR Study of
New Stable Ylides Derived from the
Reaction of Triphenylphosphine, Dialkyl
Acetylenedicarboxylates, and 5-ACYL
Meldrum’s Acid
Azizollah Habibi a , Khalil Eskandari a & Abdolali Alizadeh b
a Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
b Department of Chemistry, University of Tarbiat Modarres, Tehran,
Iran
Accepted author version posted online: 02 Mar 2012.Published
online: 19 Jun 2012.
To cite this article: Azizollah Habibi , Khalil Eskandari & Abdolali Alizadeh (2012) Synthesis and
Dynamic NMR Study of New Stable Ylides Derived from the Reaction of Triphenylphosphine, Dialkyl
Acetylenedicarboxylates, and 5-ACYL Meldrum’s Acid, Phosphorus, Sulfur, and Silicon and the Related
Elements, 187:9, 1109-1117, DOI: 10.1080/10426507.2012.668988
To link to this article: http://dx.doi.org/10.1080/10426507.2012.668988
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Phosphorus, Sulfur, and Silicon, 187:1109–1117, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.668988
SYNTHESIS AND DYNAMIC NMR STUDY OF NEW
STABLE YLIDES DERIVED FROM THE REACTION
OF TRIPHENYLPHOSPHINE, DIALKYL
ACETYLENEDICARBOXYLATES, AND 5-ACYL
MELDRUM’S ACID
Azizollah Habibi,1 Khalil Eskandari,1 and Abdolali Alizadeh2
1Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
2Department of Chemistry, University of Tarbiat Modarres, Tehran, Iran
GRAPHICAL ABSTRACT
Abstract Triphenylphosphine and dialkyl acetylenedicarboxylate react smoothly in the pres-
ence of 5-acyl Meldrum’s acid in dichloromethane at room temperature and lead to synthesis
of new stable ylide derivatives of dimethyl (5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxane-5-
yl)-3-(triphenyl-λ5-phosphanylidene) succinate. Dynamic NMR study results of rotamers are
reported and compared with the previous-related reports.
Keywords Acyl Meldrum’s acid; dialkyl acetylenedicarboxylate; three-component reaction;
triphenylphosphine; ylide
INTRODUCTION
The extension of simple and fast routes for the synthesis of widely used organic
compounds from readily available reagents is one of the major tasks in organic synthesis.
Phosphorus compounds are widely used in organic synthesis especially in the synthesis of
naturally occurringproducts anddrugcompounds.1–5 Developments of newprotocols for the
synthesis of physiologically active compounds have not been possible without phosphorus
intermediates. Organophosphorus compounds have been of interest for chemists, especially
those compounds that can form a new carbon–carbon bond. Due to their susceptibility to
participate in further reactions as active intermediates,6–8 phosphorus ylides are important
reagents which take part in interesting and valuable reactions.9–13 Extensive research has
been performed to investigate the reaction between phosphorus and other active reagents
Received 22 December 2011; accepted 16 February 2012.
Address correspondence to Azizollah Habibi, Faculty of Chemistry, Tarbiat Moallem University, No. 43,
P. Code 15719-14911, Mofateh Avenue, Tehran, Iran. E-mail: habibi@.tmu.ac.ir
1109

1110
A. HABIBI ET AL.
especially dialkyl acetylenedicarboxylate.14–17 Recently, the synthesis of new ylides bearing
in their structure, suitable functional groups that can react in a Wittig intramolecular
reaction, have been described.18–21
Meldrum’s acid (2,2-dimethyl-1,3-dioxane-4,6-dione) and its derivatives have been
broadly used in organic synthesis.22 It has interesting properties that make it a useful
molecule. It is susceptible to nucleophilic and electrophilic attack, undergoing ring-opening
reactions, along with high acidity property.23 A large number of Meldrum’s acid derivatives
have been used as intermediate in sequential organic synthesis. For instance, they are applied
for: preparation of 1,3-dicarbonyl derivatives (using 5-acyl Meldrum’s acid),24 synthesis
of different malonic ester derivatives [using 5-mono or dialkyl (aryl) Meldrum’s acid],25
and α-brominated aldehyde or ketones (by 5,5-dibromo Meldrum’s acid).26 Several reports
have been published about application of its diverse derived molecules.22,27,28
Within our studies on Meldrum’s acid and its derivatives in multicomponent reac-
tions29 herein, the synthesis of new and stable phosphorus ylides based on using 5-acyl
Meldrum’s acid (5-acyl-2,2-dimethyl-1,3-dioxane-4,6-dione) 3 is reported. The reaction of
synthesized acyl Meldrum’s acids, triphenylphosphine, and dialkyl acetylenedicarboxylate
proceeds at room temperature and leads to new stable phosphorus ylides.
RESULTS AND DISCUSSION
Firstly, acyl Meldrum’s acids derivatives were synthesized from the reaction between
Meldrum’s acid 1 and acyl halides 2 in the presence of pyridine. Obtained products were
characterized by their mp, 1H NMR, 13C NMR.24
Then, triphenylphosphine 4, dialkyl acetylenedicarboxylate 5, and acyl Meldrum’s
acid 3 readily react in dichloromethane at room temperature. After 2 h the reaction was
completed and led to new derivatives of phosphorus ylides 6 in good yields (Scheme 1).
One goal of selecting 5-acyl Meldrum’s acid was to investigate the possibility of an
internal Wittig reaction after ylide preparation. So, the reaction was continued under various
conditions, but the expected reaction did not occur. This fact indicates special stability of
synthesized ylides.
The 1H and 13C NMR spectra of the crude product clearly indicated the formation of
phosphorane 6. Any product other than 6 has not been detected by the NMR spectroscopy.
Scheme 1

SYNTHESIS AND DYNAMIC NMR STUDY OF NEW STABLE YLIDES
1111
The structures of products 6a–f were deduced from their elemental analyses, IR, 1H, 13C,
and 31P NMR spectra (as an example, 6a is represented in Figures S1–S4, Supplemental
Materials available online).
1
The H, 13C, and 31P NMR of two products (6e and f) show the presence of two
rotamers; because the structures of these ylides (6e and f) are strongly conjugated with
adjacent carbonyl group and rotation about partial double bond in 6-E and 6-Z geometrical
isomers is slow on the NMR time scale at ambient temperature (Scheme 2).
Scheme 2
1H NMR spectrum of ylides (6e and f) shows individual signal for two rotamers in
the region of CH substructure and OCH2 (or OCH3) fragment of ester.
A 1H NMR dynamic study was performed for ylide 6e in CDCl3 at ambient temper-
ature (30 ◦C). This spectrum exhibits two sharp doublets for the CH groups of (E) and (Z)
isomers. Increasing the temperature results broaden and coalescence of the CH resonances.
At 80 ◦C, a relatively broad singlet was observed for two CH groups (Figure 1).
The variable temperature spectra allowed calculating the free barrier for the restricted
C C double bond rotation in 6e. From coalescence temperature of the CH proton reso-
√
nances and using the expression kc = πꢀν/ 2, ꢀG# = 4.57Tc (10.32 + log Tc/kc), the
first-order rate constant (kc) for the dynamic NMR process in 6e is 118.5 s−1 at 353 K. Ap-
plication of the absolute rate theory with a transmission coefficient of 1 gives a free-energy
Figure 1 Variable temperature 300 MHz 1H NMR spectra C-H region of 6e in CD2Cl2.

1112
A. HABIBI ET AL.
Table 1 Activation parameters for phosphorus ylide rotamers
ꢀG#
Compound
6e
T (◦C)
(ppm)δ
ꢀν (Hz)
kc (S−1 a
)
Tc (K)
(KJ.mol−1 b
)
30
80
5.95, 6.13
6.09
54.02
118.5
353
72.79
√
akc = πꢀν/ 2; bꢀG# = 4.57Tc (10.32 + log Tc/kc).
of activation (ꢀG=) of 72.79 kJ.mol−1 (Table 1), where all known sources of errors are
estimated and included.
In order to evaluate and contrast these data with previous reports, we compared
activation parameters of the some former published data from phosphorus ylide rotamers
with our synthesized phosphorus ylides. The result of this comparison is outlined in Table 2.
A brief look at the table indicates that different published reports are consistent with each
other and prepared ylides have similar stability in rotamers.
On the basis of the previous reports about this familiar and similar reaction,30–34 we
can propose mechanism of this reaction as follow (Scheme 3). At first, triphenylphosphine
4 attacked to the acetylenic ester 5 and then, protonation of intermediate 7 occurred by
acyl Meldrum’s acid 3. Next, resulted anionic carbons 9 add to the positively charged
intermediate 8 and formed phosphorane 6 (see Scheme 3).
In conclusion, we described an efficient, simple, and one-pot three-component re-
action of triphenylphosphine and dialkyl acetylenedicarboxylate in the presence of 5-acyl
Meldrum’s acid.
Scheme 3

SYNTHESIS AND DYNAMIC NMR STUDY OF NEW STABLE YLIDES
1113
Table 2 Comparison of rotameric effect (activation parameters) for restricted rotational process around the
carbon–carbon double bond between 6e with other phosphorus ylides
δCH
(ppm)
3JPH
(Hz)
ꢀν
kc
(S−1
Tc
(K) (KJ.mol−1
ꢀG#
Phosphorus ylide
(Hz)
)
)
Ref.
5.95
6.13
12.02
12.08
54.02 118.50 353
72.8
62.5
60.6
This work
4.22
4.28
14.6
15.9
30.00
66.60 298
[30]
[30]
4.11
4.24
18.5
14.9
65.00 144.40 298
5.15
5.10
—
27.50
15.00
20.00
61.07 332
33.00 345
44.00 336
70.2
1
1
1
[31]
[32]
[32]
5.38
5.30
16.4
18.5
26.0
29.0
5.80
5.65
17.3
19.2
4.58
4.62
15.3
16.6
129.00 286.00 343
68.2
2
[33]
[34]
5.37
5.40
16.7
16.2
15.00
33.32 336
72.7
EXPERIMENTAL
Melting points were measured on an Electrothermal 9200 apparatus. IR spectra were
recorded on a FT-IR 102 MB BOMEM apparatus. Mass spectra were recorded on an AGI-
LENT TECHNOLOGY (HP)-5973 mass spectrometer operating at an ionization potential
1
of 70 eV (EI). H and 13C NMR spectra were recorded on a Bruker AVANCE-300 MHz

1114
A. HABIBI ET AL.
spectrometer employing tetramethylsilane as an internal reference. All chemicals and sol-
vents were purchased from Fluka and Merck chemical company and used as received. Table
S1 (Supplemental Materials) outlines the scope of synthesis of 6a–f.
5-acyl Meldrum’s acid derivatives 3a–c were synthesized on the basis of modified lit-
erature published procedure (see the Supplemental Materials, available online, for complete
details).24
5-(1-Hydroxyethylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (3a): Orange crystals,
mp 75–78 ◦C. Crystallization was performed with ether/hexane, yield 6.9 g, 62%.
5-(1-Hydroxypropylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (3b): Yellow crys-
tals, mp 47–50 ◦C. Crystallization was performed with ether/hexane, yield 8.05 g,
67%.
5-(1-Hydroxy-2-phenylethylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (3c): Pale
◦
yellow crystals, mp 87–90 C. Crystallization was performed with ether/hexane, yield
8.97 g, 57%.
General Procedure for the Preparation of Compounds 6
Exemplified for Dimethyl 2-(5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxane
-5-yl)-3-(triphenyl-λ5-phosphanylidene) succinate (6a). To a stirred solution of
triphenylphosphine (0.262 g, 1 mmol) and 5-acetyl-2,2-dimethyl-1,3-dioxane-4,6-dione
(0.18 g, 1 mmol) in dichloromethane (10 mL) was added dropwise a mixture of dimethyl
acetylenedicarboxylate (0.142 g, 1 mmol) in CH2Cl2 (2 mL) at room temperature and
allowed to stir for 2 h until completion (completion of the reaction was monitored by TLC).
The solvent was removed under reduced pressure and the crude product was purified by
crystallization in petroleum benzine:diethylether to give 6a as yellow crystals. Spectra of
6a are presented in the Supplemental Materials (Figures S1–S4). IR (KBr) (υmax, cm−1):
1735, 1667 (C O), 1555 (C C), 1303, 1264, 1190, 1156 (C O). 1H NMR (300.1 MHz,
CDCl3): δH 1.67 (6H, s, 2 CH3), 2.61 (3H, s, CH3), 3.74 (6H, s, 2 OCH3), 6.81 (1H, s,
CH), 7.39–7.64 (15 H, m, 3 C6H5). 13C NMR (75.47 MHz, CDCl3): δC 23.5 (CH3), 26.6
(2 CH3), 28.0 (CH), 42.6 (d, 1JPC 128.1 Hz, P C), 52.1 (2 OCH3), 91.6 (C(C O)3), 104.6
1
3
4
(C(CH3)2), 122.5 (d, JPC 99.0 Hz, Cipso), 128.4 (d, JPC 11.0 Hz, Cmeta), 131.5 (d, JPC
2.0 Hz, Cpara), 134.5 (d, 2JPC 10.0 Hz, Cortho), 165.1 (d, 3JPC 12.8 Hz, C O ester), 170.5
(d, 2JPC 13.8 Hz, C O ester), 194.4 (C O). 31P NMR (121.49 MHz, CDCl3): δp 29.4 ppm.
Anal. calcd. for C32H31O9P (590.562): C, 65.08; H, 5.29%. Found: C, 65.17; H, 5.38%.
MS: m/z (%) = 590 (M+,1), 515 (5), 429 (8), 405 (7), 368 (10), 332 (8), 293 (10), 278 (32),
277 (74), 262 (100), 236 (8), 201 (18), 183 (72), 152(20), 108 (24), 77 (23), 57 (23), 43
(51).
Diethyl 2-(5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxane-5-yl)-3-(triphenyl-
λ5-phosphanylidene) succinate (6b). IR (KBr) (υmax, cm−1): 1736, 1666 (C O),
1556 (C C), 1302, 1263, 1190, 1121 (C O). 1H NMR (300.1 MHz, CDCl3): δH 1.29 (6H,
t, 3JHH 7.1 Hz, 2 CH3), 1.71 (6H, s, 2 CH3), 2.65 (3 H, s, CH3), 4.23 (4 H, q, 3JHH 7.1 Hz, 2
CH2), 6.83 (1 H, s, CH), 7.43–7.68 (15 H, m, 3 C6H5). 13C NMR (75.47 MHz, CDCl3): δC
14.1 (2 CH3), 23.5 (CH3), 26.8 (2 CH3), 29.7 (CH), 42.9 (d, 1JPC 128.2 Hz, P C), 61.3 (2
OCH2), 91.8 (C(C O)3), 104.9 (C(CH3)2), 123.0 (d, 1JPC 99.2 Hz, Cipso), 128.7 (d, 3JPC
11.0 Hz, Cmeta), 131.5 (d, 4JPC 2.0 Hz, Cpara), 134.0 (d, 2JPC 10.2 Hz, Cortho), 165.1 (d, 4JPC
12.8 Hz, C O ester), 170.3 (d, 2JPC 13.4 Hz, C O ester), 194.6 (C O). 31P NMR (121.49
MHz, CDCl3): δP 29.3. Anal. calcd. for C34H35O9P (618.615): C, 66.02; H, 5.70%. Found:

SYNTHESIS AND DYNAMIC NMR STUDY OF NEW STABLE YLIDES
1115
C, 66.29; H, 5.52%. MS: m/z (%) = 618 (M+, 3), 615 (18), 557 (10), 433 (30), 294 (20),
278 (32), 277 (78), 262 (100), 239 (18), 220 (20), 201 (19), 183 (72), 152(20), 108 (26),
77 (27), 43 (54).
Dimethyl 2-(2,2-dimethyl-4,6-dioxo-5-propionyl-1,3-dioxane-5-yl)-3-(tri
phenyl-λ5-phosphanylidene) succinate (6c). IR (KBr) (υmax, cm−1): 1735 (C O),
1667, 1555 (C O), 1300, 1264, 1195, 1155 (C O). 1H NMR (300.1 MHz, CDCl3): δH =
1.24 (3 H, t, J 7.1 Hz, CH3), 1.67 (6 H, t, J = 7.2 Hz, 2 CH3), 1.74 (6 H, s, 2 CH3), 2.93 (2
H, q, J = 7.1 Hz, CH2), 6.81 (1 H, s, CH), 7.37–7.69 (15 H, m, 3 C6H5). 13C NMR (75.47
MHz, CDCl3): δC = 9.6 (CH2CH3), 26.8 (2 CH3), 28.1 (CH), 29.4 (2 CH2), 42.5 (d, 1JPC
=
=
1
127.95 Hz, P C), 52.1 (2 CH3), 91.6 (C(C O)3), 104.6 (C(CH3)2), 122.5 (d, JPC
3
4
99.00 Hz, Cipso), 128.2 (d, JPC 11.0 Hz, Cmeta), 130.9 (d, JPC 2.0 Hz, Cpara), 134.5 (d,
3
2
2JPC 10.0 Hz, Cortho), 165.1 (d, JPC 12.7 Hz, C O ester), 170.5 (d, JPC 13.6 Hz, C O
ester), 194.4 (C O). 31P NMR (121.49 MHz, CDCl3): δP = 29.4 ppm. Anal. calcd. for
C33H33O9P (604.589): C, 65.56; H, 5.50%. Found: C, 65.69; H, 5.42%. MS: m/z (%) =
604 (M+, 3), 530 (6), 443 (8), 420 (10), 347 (15), 293 (15), 278 (30), 277 (70), 262 (100),
201 (20), 183 (73), 152 (18), 108 (23), 77 (25), 57 (30), 43 (45).
Diethyl
2-(2,2-dimethyl-4,6-dioxo-5-propionyl-1,3-dioxane-5-yl)-3-(tri
phenyl-λ5-phosphanylidene) succinate (6d). IR (KBr) (υmax, cm−1): 1730, 1666,
1556 (C O), 1305, 1260, 1189, 1155 (C O). 1H NMR (300.1 MHz, CDCl3): δH = 1.28
3
3
(3H, t, JH,H = 7.15 Hz, CH3), 1.30 (6H, t, JH,H = 7.18 Hz, CH3), 1.74 (6H, s, 2 CH3),
2.93 (2 H, q, 3JH,H = 7.15 Hz, CH2), 4.20 (4 H, q, 3JH,H = 7.18 Hz, 2 CH2), 6.80 (1 H, s,
CH), 7.37–7.69 (15 H, m, 3 C6H5). 13C NMR (75.47 MHz, CDCl3): δC = 9.6 (CH2CH3),
26.7 (2 CH3), 26.8 (2 OCH2CH3), 29.0 (CH), 29.5 (CH2), 42.8 (d, 1JPC = 128.2 Hz, P C),
61.3 (2 CH2), 91.8 (C(C O)3), 104.8 (C(CH3)2), 122.9 (d, 1JPC = 99.24 Hz, Cipso), 127.3
3
4
2
(d, JPC 11.0 Hz, Cmeta), 130.5 (d, JPC 2.0 Hz, Cpara), 133.9 (d, JPC 10.0 Hz, Cortho),
3
2
164.8 (d, JPC 12.8 Hz, C O ester), 170.3 (d, JPC 13.8 Hz, C O ester), 194.5 (C O).
31P NMR (121.49 MHz, CDCl3): δP = 29.1 ppm. Anal. calcd. for C35H37O9P (632.642):
C, 66.45; H, 5.90%. Found: C, 66.29; H, 5.82%. MS: m/z (%) = 632 (M+, 6), 586 (5), 557
(8), 447 (22), 308 (11), 278 (30), 277 (71), 262 (100), 220 (6), 183 (61), 167 (15), 108
(20), 77 (25), 43 (44).
Dimethyl 2-(2,2-dimethyl-4,6-dioxo-5-(2-phenylacetyl)-1,3-dioxane-5-yl)-
3-(triphenyl-λ5-phosphanylidene) succinate (6e). IR (KBr), υ(cm−1): 1735, 1667,
1555 (C O), 1303, 1264, 1190, 1156 (C O). Anal. calcd. for C38H35O9P (666.659): C,
68.46; H, 5.29%. Found: C, 68.29; H, 5.12%. MS: m/z (%) = 590 (M+, 1), 515 (5), 429
(8), 405 (7), 368 (10), 332 (8), 293 (10), 278 (32), 277 (74), 262 (100), 236 (8), 201 (18),
183 (72), 152 (20), 108 (24), 77 (23), 57 (23), 43 (51).
Major: 1H NMR (300.1 MHz, CDCl3): δH = 1.40 (6H, s, 2CH3), 3.80 (3H, s, OCH3),
3.83 (3 H, s, OCH3), 5.28 (2 H, s, PhCH2), 6.20 (1H, d, JPH = 12.02 Hz, CH), 6.85–8.04
(20 H, m, 4 C6H5). 13C NMR (75.47 MHz, CDCl3): δC = 29.7 (C(CH3)2), 38.1 (PhCH2),
39.2 (d, 1JPC = 130.07 Hz, P C), 48.6, 52.1 (2 OCH3), 61.5 (C(C O)3), 104.1 (C(CH3)2),
117.4 (d, 1JPC = 99.02 Hz, Cipso), 125.1–137.7 (4 C6H5), 169.1 (d, 2JPC = 14.0 Hz, PCCO),
175.6, 209.3 (C O). 31P NMR (121.49 MHz, CDCl3): δP = 23.7 ppm.
Minor: 1H NMR (300.1 MHz, CDCl3): δH = 1.36 (6H, s, 2CH3), 3.37 (3H, s, OCH3),
3.78 (3H, s, OCH3), 4.95 (2 H, s, PhCH2), 5.92 (1 H, d, JPH 12.08 Hz, CH), 6.85–8.04
(20 H, m, 4 C6H5). 13C NMR (75.47 MHz, CDCl3): δC = 29.2 (C(CH3)2), 38.2 (PhCH2),
45.9 (d, 1JPC = 130.02 Hz, P C), 48.6, 57.2 (2 OCH3), 62.6 (C(C O)3), 104.3 (C(CH3)2),
120.4 (d, 1JPC = 99.02 Hz, Cipso), 125.1–137.7 (4 C6H5), 172.1 (d, 2JPC = 14.0 Hz, PCCO),
175.8 (C O), 210.3 (C O). 31P NMR (121.49 MHz, CDCl3): δP = 23.1 ppm.

1116
A. HABIBI ET AL.
Diethyl 2-(2,2-dimethyl-4,6-dioxo-5-(2-phenylacetyl)-1,3-dioxane-5-yl)-3-
(triphenyl-λ5-phosphanylidene) succinate (6f). IR (KBr), υ(cm−1): 1722, 1662,
1587 (C O), 130, 1259, 1195, 1199 (C O). Anal. calcd. for C38H35O9P (694.713): C,
69.16; H, 5.66%. Found: C, 68.98; H, 5.62%. MS: m/z (%) = 590 (M+, 1), 515 (5), 429
(8), 405 (7), 368 (10), 332 (8), 293 (10), 278 (32), 277 (74), 262 (100), 236 (8), 201 (18),
183 (72), 152(20), 108 (24), 77 (23), 57 (23), 43 (51).
Major: 1H NMR (300.1 MHz, CDCl3): δH = 0.48 (3 H, t, 3JH,H = 7.16 Hz, CH2CH3),
1.49 (3 H, t, 3JH,H = 7.16 Hz, CH2CH3), 1.36 (6 H, s, C(CH3)2), 4.11 (2 H, q, 3JH,H = 7.16
Hz, OCH2), 4.25 (2 H, q, 3JH,H = 7.16 Hz, OCH2), 5.27 (2 H, s, PhCH2), 6.15 (1H, d, JPH
=
12.60 Hz, CH), 6.83–8.00 (20 H, m, 4 C6H5). 13C NMR (75.47 MHz, CDCl3): δC = 13.4
1
(CH2CH3), 14.0 (CH2CH3), 27.7 (CH), 29.9 (C(CH3)2), 38.0 (PhCH2), 40.0 (d, JPC
=
130.07 Hz, P C), 48.6, 58.8 (OCH2), 60.8 (OCH2), 63.1 (C(C O)3), 104.1 (C(CH3)2),
118.5–137.9 (4 C6H5), 168.7 (d, 2JPC = 12.75 Hz, PCCO), 175.3, 209.6 (C O). 31P NMR
(121.49 MHz, CDCl3): δP = 23.9 ppm.
Minor: 1H NMR (300.1 MHz, CDCl3): δH = 0.30 (3H, t, 3JH,H = 7.15 Hz, CH2CH3),
1.29 (3H, t, 3JH,H = 7.16 Hz, CH2CH3), 1.30 (6 H, s, C(CH3)2), 3.50 (2 H, q, 3JH,H = 7.15
Hz,OCH2), 3.70 (2 H, q, 3JH,H = 7.15 Hz,OCH2), 5.30 (2 H, s, PhCH2), 5.80 (1 H, d, JPH
=
12.65 Hz, CH), 6.83–8.00 (20 H, m, 4 C6H5). 13C NMR (75.47 MHz, CDCl3): δC = 12.9
1
(CH2CH3), 15.3 (CH2CH3), 28.1 (CH), 29.8 (C(CH3)2), 38.0 (PhCH2), 44.5 (d, JPC
=
130.07 Hz, P C), 48.6, 57.1 (OCH2), 58.9 (OCH2), 63.1 (C(C O)3), 104.1 (C(CH3)2),
118.5–137.9 (4 C6H5), 168.7 (d, 2JPC = 12.75 Hz, PCCO), 175.3, 208.9 (C O). 31P NMR
(121.49 MHz, CDCl3): δP = 23.9 ppm.
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