Probing the group tolerance of a Li/Cl phosphinidenoid complex using alkenyl-substituted aldehydes

Article abstract of DOI:10.1021/om300177c

Reaction of the Li/Cl phosphinidenoid pentacarbonyltungsten complex 2 (R = CH(SiMe₃)₂) with unsaturated aldehydes 3, 4, 9, 10, and 13 yielded the new oxaphosphirane complexes 5, 7, 11, 12, and 14 and thus revealed a clear preference for C=O vs C=C bond addition (i) and for 1,2- vs 1,4 addition (ii). Complexes were characterized by NMR, IR spectroscopy, and mass spectrometry and, in the case of 14a, by single-crystal X-ray analysis.

Full text of DOI:10.1021/om300177c

Article
pubs.acs.org/Organometallics
Probing the Group Tolerance of a Li/Cl Phosphinidenoid Complex
Using Alkenyl-Substituted Aldehydes
Rainer Streubel,* Melina Klein, and Gregor Schnakenburg
Institut fur Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universitat Bonn, Gerhard-Domagk-Straße 1,
̈
̈
53121 Bonn, Germany
S
* Supporting Information
ABSTRACT: Reaction of the Li/Cl phosphinidenoid pentacarbonyltungsten complex 2 (R = CH(SiMe3)2) with unsaturated
aldehydes 3, 4, 9, 10, and 13 yielded the new oxaphosphirane complexes 5, 7, 11, 12, and 14 and thus revealed a clear preference
for CO vs CC bond addition (i) and for 1,2- vs 1,4 addition (ii). Complexes were characterized by NMR, IR spectroscopy,
and mass spectrometry and, in the case of 14a, by single-crystal X-ray analysis.
organic iodides was also observed. Recent results obtained from
hosphanides I and their complexes II (Scheme 1) are key
Preagents and ligands in main-group and transition-metal the reaction of an Li/Cl phosphinidenoid complex with N-Me-
substituted 3-thienyl imine supports the latter reactivity, as a
nucleophilic formal [4 + 1] cycloaddition was concluded on
the basis of DFT calculations.9 Although these investigations, in-
cluding a recent study on cyclic ketones,10 provided some insights,
the reactivity of M/X phosphinidenoid complexes is still largely
unexplored; e.g., the quest for the reaction course of such formal
[2 + 1] cycloaddition reactions is far from being solved.
Here, we report preliminary results on reactions of the Li/Cl
phosphinidenoid complex 2 with aldehydes possessing a remote
or conjugated alkenyl moiety: i.e., probing the functional group
tolerance of such phosphinidenoid complexes and the course of
cycloaddition.
Scheme 1. Phosphanides I and Phosphinidenoids III and
Their Transition-Metal Complexes II and IV
Legend: R, R′ = organic substituents, X = halogen, M = main-group
metal, MLn = transition-metal complex.
chemistry alike: e.g., lithium phosphanides1 enable the formation
of single and/or multiple bonds between phosphorus and carbon
and/or metal atoms. In contrast, phosphinidenoids III possessing a
functional group X (Scheme 1) have been neither firmly established
nor much used and have been proposed only as intermediates2
and/or precursors for phosphinidenes.3 Interestingly, although
they are also highly reactive, transient terminal phosphinidene com-
plexes have become important building blocks during the last few
decades.4 Recently, the first protocol to generate Li/X phosphin-
idenoid transition-metal complexes IV (X = F,5a Cl;5b
R = CH(SiMe3)2) was reported, which revealed the particular
importance of the presence of 12-crown-4. So far, the nature of the
stabilization of this new reactive intermediate is still unclear.
Preliminary results on the reactivity of IV (X = Cl) toward
nitriles, alkynes, and aldehydes pointed to a phosphinidene
complex like behavior,5b but a nucleophilic reactivity5−8 toward
First, the reaction of Li/Cl phosphinidenoid complex 2,8 obtained
via chlorine/lithium exchange in complex 19 in the presence of 12-
crown-4, with aldehydes 3 and 4 possessing a pendant alkenyl moiety
was investigated. Under these conditions the diastereomeric oxaphos-
phirane complexes 5a,b and 7a,b (Scheme 2) were obtained. In both
cases, it was observed that byproducts in small amounts (6, 10%; 8,
1
6%) were formed (6, δ(31P) 21.4, J(W,P) = 290.9 Hz; 8, δ(31P)
20.2, 1J(W,P) = 290.4 Hz) that exhibited very similar 31P{1H} NMR
parameters. Unfortunately, the latter could not be separated using
column chromatography or crystallized. Nevertheless, mixtures were
Received: March 2, 2012
Published: June 15, 2012
© 2012 American Chemical Society
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Scheme 2. Synthesis of Oxaphosphirane Complexes 5a,b, 7a,b, 11, 12, and 14a,b
obtained that allowed us to record and unambiguously assign the
NMR data of the major isomers 5a and 7a.
and are formed due to this phenomenon. On the other hand, this
phenomenon was only observed for C,C′-disubstituted oxaphos-
phirane derivatives, which are sterically more demanding.
Then, reactions of complex 2 with the α,β-unsaturated
aldehydes 9 and 10 were studied, which selectively furnished
oxaphosphirane complexes 11 (δ(31P) 36.0, 1J(W,P) = 301.7 Hz)
CONCLUSIONS
■
1
and 12 (δ(31P) 38.4, J(W,P) = 304.9 Hz) (Scheme 2). As
This first study on reactions of a Li/Cl phosphinidenoid
complex with bifunctional π-substrates revealed the following:
these reactions were very selective, no indications of products
steming from formal [4 + 1] cycloaddition reactions were
obtained, thus showing a clear π-substrate preference for the
CO bond. Complexes 11 and 12 could not be purified via
column chromatography, as partial decomposition occurred, but
filtration and washing at low temperature proved to be successful
and yielded 11 as a solid and 12 as an oil; for structurally relevant
NMR data see Table 1.
• an excellent π selectivity toward aldehydes possessing
additional CC bonds in the substituent with a clear
preference for the CO bond (high group tolerance)
• a clear preference for formal 1,2- vs 1,4-addition reactions
and, hence, pronounced nucleophilic character
• a weak basicity of the phosphorus center
In a preliminary investigation the benzyl-substituted aldehyde
13 was used as a case in point for substrates that possess some-
what acidic protons at the α-carbon atom. However, the reac-
tion of complex 2 with 13 proceeded smoothly to the diastereomeric
oxaphosphirane complexes 14a,b. Here again, small amounts of
When the first and second aspects are combined, it provides
good evidence that the formation of the oxaphosphirane ring
proceeds via an initial nucleophilic attack of the phosphorus of
the phosphinidenoid complex at the aldehyde carbon atom.
Nevertheless, further studies will be necessary to achieve a
detailed understanding of ring-forming reactions.
1
a byproduct were observed (9%) (15, δ(31P) 21.7, J(W,P) =
300.7 Hz) (Scheme 2) which could not be separated via column
chromatography.
EXPERIMENTAL SECTION
■
The molecular structure of complex 14a was confirmed by a
single-crystal X-ray diffraction study, but other than a disorder
of the phenyl ring (76% vs 24%), it did not reveal any peculiar
distances or angles (Figure 1). The s-cis conformation of the
CH(SiMe3)2 group (relative orientation of C−H and P−W at
the exocyclic P−C bond) is also common for the previously
reported oxaphosphirane complex X-ray structures. As it was
observed recently7 that this particular arrangement may lead to
a P−C atropisomerism in oxaphosphirane complexes, one might
be tempted to speculate that the observed byproducts (in the case
of 5a,b, 7a,b, and 14a,b) are oxaphosphirane complexes as well
All reactions were carried out under an inert gas atmosphere using
purified and dried argon and standard Schlenk techniques. Solvents
were dried over sodium wire/benzophenone and distilled under argon.
NMR data were recorded on a Bruker DMX 300 spectrometer at
30 °C using C6D6 as solvent and internal standard; chemical shifts are
given in ppm relative to tetramethylsilane (1H, 300.13 MHz; 13C,
75.5 MHz; 29Si, 59.6 MHz), and 85% H3PO4 (31P, 121.5 MHz). Mass
spectra were recorded on a MAT 95 XL Finnigan (EI, 70 eV, 184W)
spectrometer, and IR spectra were recorded on a Thermo Nicolet 380 FT-
IR spectrometer; selected data are given. Melting points were determined
using a Buchi type S apparatus; the values are not corrected. Elemental
̈
analyses were performed by using an Elementar VarioEL instrument.
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1
Table 1. 31P, H, and 13C NMR Data (C6D6) of the Major Isomers of Complexes 5, 7, 11, 12, and 14
Complex 5a. “Yield” of the mixture of 5a,b and 6 (69:21:10): 269 mg
(0.49 mmol, 58%). Analytical data obtained from this mixture are as
follows. 1H NMR: δ 0.12 (s, 18H, Si(CH3)3); 1.09 (s, 1H, CH(Si-
(CH3)3)2); 1.86−1.54 (m, 2H, CH2); 2.28−2.03 (m, 2H, CH2); 3.03 (t,
1H, 3J(H,H) = 6.1 Hz, CH(P)(O)); 5.10−4.90 (m, 2H, CH2); 5.78−5.57
(m, 1H, CH). 13C{1H} NMR: δ 1.2 (d, 3J(P,C) = 4.8 Hz, Si(CH3)3); 1.4
(s, Si(CH3)3); 30.5 (d, 3J(P,C) = 6.5 Hz, CH2); 30.8 (d, 3.0 Hz, 2J(P,C) =
1
3.0 Hz, CH2); 29.2 (d, J(P,C) = 17.7 Hz, CH(Si(CH3)3)2); 58.9 (d,
1J(P,C) = 31.1 Hz, CH(P)(O)); 116.2 (s, CH2CH); 136.9 (s, CH2
C(H)); 195.8 (d, 2J(P,C) = 8.4 Hz, cis-CO); 197.7 (d, 2J(P,C) = 33.7 Hz,
2
trans-CO). 29Si{1H} NMR: δ −1.69 (d, J(P,Si) = 5.1 Hz); 0.06 (d,
2J(P,Si) = 8.0 Hz). 31P{1H}NMR: δ 29.6 (1J(W,P) = 299.2 Hz). IR
(Nujol, selected data): ν
̃
(cm−1) 1255 (s), 1459 (m), 1641 (w), 1953 (s),
1988 (m), 2076 (s), 2854 (s), 2924 (s), 2959 (s). MS (EI, 184W): m/z
598.1 (5) [M]•+, 514.0 (20) [M − 3CO]+, 486.0 (55) [M − 4CO]+,
458.1 (25) [M − 5CO]+, 430.1 (25) [M − 3CO − C5H8O]+, 402.0 (20)
[M − 4CO − C5H8O]+, 384.0 (30) [M − 5CO − HSi(CH3)3]+, 374.0
(10) [M − 5CO − C5H8O]+, 358.0 (30) [M − 5CO − Si(CH3)3 −
C2H3]+, 341.0 (20) [M − 3CO − CH2 − CH(Si(CH3)3)2]+, 299.0 (10)
[M − 5CO − CH(Si(CH3)3)2]+, 129.1 (5) [CH(Si(CH3)3)2]+, 73.1
(100) [Si(CH3)3]+. Anal. Calcd for C17H27O6PSi2W (598.4 g/mol): C,
34.12; H, 4.55. Found: C, 34.57; H, 4.60.
Figure 1. Molecular structure of 14a. There is 2-fold disorder in the
orientation of the phenyl ring (the 76% site is shown); because of the
great similarity only one data set is given. Hydrogen atoms are omitted
for clarity. Selected bond lengths (Å) and angles (deg): W−P =
2.4635(13), P−O1 = 1.669(4), C1−O1 = 1.491(8), P−C1 = 1.800(7);
P−O1−C1 = 69.2(3), C1−P−O1 = 50.8(3), O1−C1−P = 60.1(3).
Complex 5b. 31P{1H} NMR: δ 34.8 (1J(W,P) = 294.6 Hz).
Complex 7a. “Yield” of the mixture of 7a,b and 8 (85:9:6): 325 mg
(0.48 mmol, 56%). Analytical data obtained from this mixture are as
1
4
follows. H NMR: δ 0.20 (d, 9H, J(P,H) = 1.9 Hz, Si(CH3)3); 0.33
(s, 9H, Si(CH3)3); 1.17 (s, 1H, CH(Si(CH3)3)2); 1.20−1.45 (m, 10H,
CH2); 1.49−1.61 (m, 2H, CH2); 1.61−1.90 (m, 2H, CH2); 2.00−2.14
(m, 2H, CH2CHCH2); 3.05−3.15 (m, 1H, CH(P)(O)); 5.02−5.17
(m, 2H, CH2CH); 5.79−5.95 (m, 1H, CH2CH). 13C{1H} NMR:
Complexes 5, 7, 11, 12, and 14. To a freshly prepared solution
of 2 (0.47 g, 0.85 mmol) in Et2O (15 mL) were added the following
aldehydes: 101.2 μL of 3 (86.3 mg, 1.2 equiv), 0.20 mL of 4 (172.5
mg, 1.2 equiv), 84.9 μL of 9 (71.8 mg, 1.2 equiv), 98.9 μL of 10 (86.2
mg, 1.2 equiv), and 99.7 μL of 13 (102.6 mg, 1.0 equiv). The reaction
mixture was warmed to room temperature (except for 11 and 12,
which were warmed to only −20 °C), and the solvent was removed in
vacuo (∼10−2 mbar). From the residues the products 5, 7, 12, and 14
were extracted with n-pentane at ambient temperature and in the case
of complex 11 at −20 °C. Complexes 5, 7, and 14 were purified by
column chromatography (Al2O3, −20 °C, petroleum ether); products
5, 7 and 14 were all obtained and characterized as mixtures (ratios are
given below).
3
3
δ 1.2 (d, J(P,C) = 3.9 Hz, Si(CH3)3); 1.8 (d, J(P,C) = 2.6 Hz,
Si(CH3)3); 30.4 (d, 1J(P,C) = 16.2 Hz, CH(Si(CH3)3)2); 29.7
(s, CH2); 29.4 (s, CH2); 29.7 (s, CH2); 29.3 (s, CH2); 26.7 (s, CH2);
26.6 (s, CH2); 31.6 (d, 2J(P,C) = 2.8 Hz, CH2CH(O)P); 34.2
1
(s, CH2CHCH2); 60.0 (d, J(P,C) = 30.7 Hz, CH(P)(O)); 114.5
(s, CH2CH); 139.2 (s, CH2CH); 195.8 (d, 2J(P,C) = 8.4 Hz, cis-
CO); 197.8 (d, 2J(P,C) = 33.6 Hz, trans-CO). 29Si{1H} NMR: δ −1.9
2
2
(d, J(P,Si) = 5.1 Hz), −0.1 (d, J(P,Si) = 8.0 Hz). 31P{1H} NMR: δ
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28.5 (1J(W,P) = 297.3 Hz). IR (Nujol, selected data): ν
̃
(cm−1) 1254 (s),
486.0 (100) [M − H − 2CO − C7H7]+, 458.0 (25) [M − H − 3CO −
C7H7]+, 430.0 (30) [M − H − 4CO − C7H7]+, 402.0 (21) [M − H −
5CO − C7H7]+, 383.9 (31) [M − 2Si(CH3)3 − CO − C6H5 + H]2+,
358.0 (31) [M − Si(CH3)3 − 4CO − C7H7]+, 193.1 (35) [C8H8O −
Si(CH3)3]+, 91.0 (10) [C7H7]+, 73.0 (75) [Si(CH3)3]+. Anal. Calcd for
C20H27O6PSi2W (634.4 g/mol): C, 37.86; H, 4.29. Found C 37.91; H, 4.44.
Complex 14b. 31P{1H} NMR: δ 31.8 (1J(W,P) = 296.0 Hz).
1459 (m), 1641 (w), 1953 (s), 1988 (m), 2076 (s); 2854 (s) 2925 (s),
2958 (s). MS (EI, 184W): m/z 542.1 (5) [M − 5CO]+, 513.9 (15)
[M − C11H20O]+, 486.0 (100) [M − CO − C11H20O]+, 458.0 (30)
[M − 2CO − C11H20O]+, 432.0 (20) [M − 3CO − C11H20O]+, 402.0
(10) [M − 4CO − C11H20O]+, 358.0 (20) [M − W(CO)5]+, 111.1
(18) [C8H15]+, 97.1 (25) [C7H13]+, 83.1 (30) [C6H11]+, 73.1 (100)
[Si(CH3)3]+, 69.1 (35) [C5H9]+, 55.1 (55) [C4H7]+. Anal. Calcd for
C23H39O6PSi2W (682.5 g/mol): C, 40.47; H, 5.76. Found: C, 41.66;
H, 6.22.
Crystal Data for 14a. Suitable single crystals of 14a were obtained
from a concentrated n-pentane solution cooled to −20 °C. Data were
collected with a Nonius KappaCCD diffractometer equipped with a
low-temperature device at 100 K by using graphite-monochromated
Mo Kα radiation (λ = 0.710 73 Å). The structure was solved by
Patterson methods (SHELXS-97)13a and refined by full-matrix least-
squares on F2 (SHELXL-97).13b Crystal data: C20H27O6PSi2W, Mr =
634.4, colorless, crystal dimensions 0.12 × 0.10 × 0.01 mm3, triclinic,
Complex 7b. 31P{1H} NMR: δ 33.9 (1J(W,P) = 293.5 Hz).
1
Complex 11. Yield: 259 mg (0.44 mmol, 52%). Mp: 55 °C; H
NMR: δ 0.10 (s, 9H, Si(CH3)3); 0.12 (s, 9H, Si(CH3)3); 1.13 (s, 1H,
3
CH(Si(CH3)3)2); 1.51 (d, J(H,H) = 6.6 Hz, 3H, CHCH(CH3);
3.51 (d, 3J(H,H) = 5.6 Hz, 1H, CH(P)(O)); 5.40−5.53 (m, 1H,
CHCH(CH3)); 5.71−5.87 (m, 1H, CHCH(CH3)). 13C{1H}
NMR: δ 1.2 (d, 3J(P,C) = 4.2 Hz, Si(CH3)2); 1.7 (d, 3J(P,C) = 2.3 Hz,
Si(CH3)2); 17.9 (d, 4J(P,C) = 2.3 Hz, CHCH(CH3)); 31.1 (d,
1J(P,C) = 19.2 Hz, CH(Si(CH3)3)2); 59.3 (d, 1J(P,C) = 32.4 Hz,
space group P1, Z = 2, a = 9.1156(9) Å, b = 10.8683(7) Å, c =
̅
13.3557(13) Å, α = 77.712(6)°, β = 81.120(4)°, γ = 88.288(6)°, V =
1277.3(2) Å3, Dexptl = 1.649 g cm−3, μ = 4.708 mm−1, T = 123(2) K,
transmission factors (minimum/maximum) 0.6019/0.9544, analytical
2
absorption correction based on the indexing of the crystal faces, 2θmax
=
CH(P)(O)); 125.5 (s, CH(CH3)CH); 131.4 (d, J(P,C) = 9.6 Hz,
CHCH(CH3)); 195.8 (d, 2J(P,C) = 8.4 Hz, cis-CO); 197.8 (d,
54.0°, 5437 unique data, Rint = 0.0499, R1 (for I > 2σ(I)) = 0.0369,
wR2 (for all data) = 0.0797, final R = 0.0369, goodness of fit 0.986,
ΔF(maximum/minimum) = 1.693/−2.082 e Å−3.
2J(P,C) = 34.4 Hz, trans-CO). 29Si{1H} NMR: δ −0.97 (d, J(Si,P) =
2
5.4 Hz); 0.57 (d, 2J(Si,P) = 7.9 Hz). 31P{1H} NMR: δ 36.0 (1J(W,P) =
301.7 Hz). IR (KBr, selected data): ν
̃
(cm−1) 967 (m), 1253 (s), 1376
(m), 1449 (m), 1915 (s), 2076 (s), 2901 (m), 2917 (m), 2956 (s). MS
(EI, 184W): m/z 583.9 (18) [M]•+, 555.9 (10) [M − CO]+, 527.9 (5)
[M − 2CO]+, 513.8 (20) [M − C4H6O]+, 499.9 (8) [M − 3CO]+,
485.9 (80) [M − CO − C4H6O]+, 457.9 (40) [M − 2CO − C4H6O]+,
443.9 (20) [M − 5CO]+, 429.9 (50) [M − 3CO − C4H6O]+, 401.9
(30) [M − 4CO − C4H6O]+, 357.9 (40) [M − 3CO − C4H6O −
Si(CH3)3 − H]+, 353.8 (75) [M − 3CO − 2Si(CH3)3]+, 73.0 (60)
[Si(CH3)3]+. Anal. Calcd for C16H25O6PSi2W (584.4 g/mol): C,
32.89; H, 4.31. Found: 32.58, 4.75.
ASSOCIATED CONTENT
■
S
* Supporting Information
A CIF file giving crystallographic data for 14a. This material is
available free of charge via the Internet at http://pubs.acs.org.
Crystallographic data of 14a have also been deposited at the
Cambridge Crystallographic Data Centre under the file number
CCDC 868282. These data can be obtained free of charge from
the Cambridge Crystallographic Data Centre via www.ccdc.
cam.ac.uk/data_request/cif.
1
Complex 12. Yield: 261 mg (0.44 mmol, 51%). H NMR: δ 0.15
(s, 9H, Si(CH3)3); 0.16 (s, 9H, Si(CH3)3); 1.16 (s, 1H, CH(Si-
(CH3)3)2); 1.49−1.56 (m, 3H, C(CH3)CH(CH3)); 1.65 (s, 3H,
C(CH3)CH(CH3)); 3.49 (s, br, 1H, CH(P)(O)); 5.64−5.72
AUTHOR INFORMATION
■
3
(m, 1H, C(CH3)CH(CH3)). 13C{1H} NMR: δ 1.5 (d, J(P,C) = 4.1
Corresponding Author
*E-mail: r.streubel@uni-bonn.de. Fax: (+) 49-228-73-9616.
3
3
Hz, Si(CH3)2); 2.0 (d, J(P,C) = 2.3 Hz, Si(CH3)2); 12.8 (d, J(P,C) =
2.8 Hz, C(CH3)CH(CH3)); 14.2 (s, C(CH3)CH(CH3); 31.9 (d,
1J(P,C) = 19.9 Hz, CH(Si(CH3)3)2); 61.6 (d, 1J(P,C) = 26.1 Hz,
Notes
2
CH(P)(O)); 122.5 (d, J(P,C) = 9.0 Hz, CH(CH3)C(CH3)); 129.2
The authors declare no competing financial interest.
(d, 2J(P,C) = 2.0 Hz, C(CH3)CH(CH3)); 195.8 (d, 2J(P,C) = 8.3 Hz,
cis-CO); 197.7 (d, J(P,C) = 34.8 Hz, trans-CO). 29Si{1H} NMR: δ
2
ACKNOWLEDGMENTS
−1.33 (d, 2J(P,Si = 5.5 Hz); 0.61 (d, 2J(P,Si) = 7.9 Hz). 31P{1H} NMR: δ
■
̃
38.4 (1J(W,P) = 304.9 Hz). IR (KBr, selected data): ν (cm−1) 937 (m),
We thank the Deutsche Forschungsgemeinschaft (STR 411/
26-1) and the COST action CM0802 “PhoSciNet” for financial
support. G.S. thanks Prof. A. C. Filippou for support.
1253 (s), 1381 (m), 1437 (m), 1620 (v), 1660 (v), 1913 (s), 2075 (s),
2903 (m), 2931 (m), 2955 (s); MS (EI, 184W): m/z 598.0 (20) [M]•+,
570.0 (10) [M − CO]+, 542.0 (5) [M − 2CO]+, 514.0 (20) [M − 3CO]+,
486.0 (100) [M − 4CO]+, 458.0 (45) [M − 5CO]+, 430.0 (45) [M −
4CO − C4H8]+, 402.0 (35) [M − 5CO − C4H8]+, 383.9 (55) [M −
CH(Si(CH3)3)2 − C4H7]+, 358.0 (45) [M − 5CO − Si(CH3)3 − C4H7]+,
73.0 (70) [Si(CH3)3]+.
REFERENCES
■
(1) (a) Smith, J. D. Angew. Chem. 1998, 110, 2181−2183; Angew.
Chem., Int. Ed. 1998, 3, 2071−2073. (b) Izod, K. Adv. Inorg. Chem.
2000, 50, 33. (c) Rabe, G. W.; Liable-Sands, L. M.; Rheingold, A. L.
Inorg. Chim. Acta 2002, 329, 151−154. (d) Izod, K.; Stewart, J. C.;
Cleggm, W.; Harrington, R. W. Dalton Trans. 2007, 257−264.
(e) Pauer, F.; Power, P. P. In Lithium Chemistry: A Theoretical and
Experimental Overview; Sapse, A. M., Schleyer, P. v. R., Eds.; Wiley:
New York, 1994; p 361.
Complex 14a. “Yield” of the mixture of 14a,b and 15 (75:16:9):
324 mg (0.51 mmol, 60%). Mp: 98 °C. Analytical data obtained from
1
this mixture are as follows. H NMR: δ 0.02 (s, 9H, Si(CH3)3); 0.07
(s, 9H, Si(CH3)3); 1.10 (s, 1H, CH(Si(CH3)3)2); 2.84−3.09 (m, 2H,
CH2); 3.28 (dd, 1H, 2+4J(H,H) = 5.4 Hz, 7.5 Hz, CH(P)(O)); 7.03−
7.08 (m, 1H, CH-Ar); 7.09−7.14 (m, 2H, CH-Ar); 7.20−7.26 (m, 2H,
3
CH-Ar). 13C{1H} NMR: δ 1.1 (d, J(P,C) = 4.3 Hz, Si(CH3)3); 1.8
(2) (a) Yoshifuji, M.; Shima, I.; Inamoto, N.; Hirotsu, K.; Higuchi, T.
J. J. Am. Chem. Soc. 1981, 103, 4587−4589. (b) Couret, C.; Escudie,
(d, 3J(P,C) = 2.3 Hz, Si(CH3)3); 30.7 (d, 1J(P,C) = 16.9 Hz,
CH(Si(CH3)3)2); 37.9 (d, 2J(P,C) = 3.4 Hz, CH2); 60.5 (d, 1J(P,C) =
30.1 Hz, CH(P)(O)); 127.4 (s, CH-Ar); 129.1 (s, CH-Ar); 129.2 (s,
́
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Satge,
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3
2
CH-Ar); 137.1 (d, J(P,C) = 8.2 Hz, C−Ar); 195.9 (d, J(P,C) = 8.4
Hz, cis-CO); 196.2 (d, 2J(P,C) = 33.6 Hz, trans-CO). 29Si{1H} NMR:
δ −1.88 (d, 2J(P,Si) = 4.9 Hz); −0.07 (d, 2J(P,Si) = 8.1 Hz). 31P{1H}
(3) (a) Schmidt, U. Angew. Chem. 1975, 87, 535−540. (b) Li, X.; Lei,
D.; Chiang, M. Y.; Gaspar, P. P. J. Am. Chem. Soc. 1992, 114, 8526.
(c) Li, X.; Weissman, S. I.; Lin, T. S.; Gaspar., P. P. J. Am. Chem. Soc.
1994, 116, 7899. (d) Bucher, G.; Borst, M. L. G.; Ehlers, A. W.;
Lammertsma, K.; Ceola, S.; Huber, M.; Grote, D.; Sander, W. Angew.
Chem., Int. Ed. 2005, 44, 3289−3293.
̃
NMR: δ 29.8 (1J(W,P) = 300.7 Hz). IR (KBr, selected data): ν (cm−1)
726 (w), 1255 (s), 1454 (m), 1496 (m), 1930 (s), 1997 (s), 2077 (s),
2856−2924 (w), 2960 (s), 3034 (w). MS (EI, 184W): m/z 634.1 (3) [M]•+,
514.0 (40) [M − H − CO − C7H7]+, 488.0 (82) [M − 2Si(CH3)3] +,
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