Free and supported phosphorus ylides as strong neutral bronsted bases

Full text of DOI:10.1021/jo9822030

J . Org. Chem. 1999, 64, 3741-3744
3741
Sch em e 1
F r ee a n d Su p p or ted P h osp h or u s Ylid es a s
Str on g Neu tr a l Br øn sted Ba ses
Ste´phanie Goumri-Magnet,† Olivier Guerret,†
Heinz Gornitzka,† J ean Bernard Cazaux,‡ Dennis Bigg,§
Francisco Palacios, and Guy Bertrand*,†
Laboratoire de Chimie de Coordination,
205 route de Narbonne, 31077 Toulouse Cedex, France,
Expansia S. A., route d’Avignon, BP 6,
Sch em e 2
30390 Aramon Cedex, France, Institut Henri Beaufour,
17, avenue Henri descartes,
92350 Le Plessis Robinson, France, and Facultad de
Farmacia, Universidad del Pais Vasco, Aparrado 450,
01080 Vitoria, Spain
Received November 3, 1998
followed by extraction with pentane, offers the salt-free5
ylide 2 (no trace of alkali iodide was detected by elemen-
tal analysis) (Scheme 1).
In tr od u ction
Eva lu a tion of th e p Ka Va lu e of 2H+. The most
common strong neutral bases used in organic synthesis
are, by order of increasing power, tertiary amines, proton
sponges,6 guanidines7 (mainly DBN and DBU), Verkade’s
phosphatrane 5,8 and the polyphosphazene 1. 31P NMR
spectroscopy was used to evaluate the pKa value of 2H+.
In THF-d8, the 31P NMR chemical shift of 2H+ (+65 ppm)
is not affected by addition of a stoichiometric amount of
DBU or DBN. More interestingly, phosphatrane 5 was
also unable to deprotonate 2H+, while 1 quantitatively
(according to 31P NMR spectroscopy) reacted with 2H+
affording 1H+ and 2. Therefore, we can assume that the
pKa value of 2H+ is intermediate between those of 5H+
and 1H+ (268 and 281 in THF, respectively). Even though
the pKa values of 1H+, 2H+, and 5H+ are very close, no
equilibria were detected by 31P NMR spectroscopy (Scheme
2). Note that the amino substituents at phosphorus play
an important role on the pKa value; for comparison, the
In the early 1990s, Schwesinger reported that phos-
phazenes such as 1 (namely P4-t-Bu) are nonnucleophilic
very strong bases.1 They have found numerous applica-
tions in organic synthesis,2 but their high molecular
weight and cost are drawbacks for their extensive use.
Here, we report that simple ylides3 such as P-tris-
(dimethylamino)-C-dimethylphosphonium ylide 2 can be
conveniently used in place of P4-t-Bu; moreover, a sup-
ported version 3 of this type of base is also presented.4
+
pKa value of Ph3PCH3 is only around 19.3
Syn th etic Uses of th e Ylid e 2. We first tested
N-functionalization reactions of lactam 6a and benzodi-
azepine 7a . Addition at -78 °C of a slight excess (5%) of
a freshly prepared THF solution of the ylide 2 to THF
solutions of 6a and 7a , followed by addition of the
alkylating reagent (CH3I, t-BuO2CCH2Br, PhCH2Br), led
to the expected products 6b-d and 7b-d , respectively
(Scheme 3). According to NMR spectroscopy, the reactions
were quantitative; the isolated yields obtained after
purification on column chromatography were not opti-
mized. Of particular interest, the phosphonium salt
Resu lts a n d Discu ssion
Syn th esis of th e Ylid e 2. Alkylation of tris(dimeth-
ylamino)phosphine 4 with the 2-iodopropane leads to the
phosphonium salt 2H+I-, which has been isolated in 91%
yield as an air-stable white solid storable for months at
room temperature. Treatment of this salt with a strong
base, such as n-BuLi or alkaline hydrides in dry THF,
† Laboratoire de Chimie de Coordination.
‡ Expansia S. A.
§ Institut Henri Beaufour.
(1) (a) Schwesinger, R.; Schlemper, H. Angew. Chem., Int. Ed. Engl.
1987, 26, 1167. (b) Schwesinger, R. Nachr. Chem. Technol. Lab. 1990,
38, 1214. (c) Schwesinger, R.; Hasenfratz, C.; Schlemper, H.; Walz,
L.; Peters, E. M.; Peters, K.; v. Schnering, H. G. Angew. Chem., Int.
Ed. Engl. 1993, 32, 1361. (d) Schwesinger, R.; Schlemper, H.; Hasen-
fratz, C.; Willaredt, J .; Dambacher, T.; Breuer, T.; Ottaway, C.;
Fletschinger, M.; Boele, J .; Fritz, H.; Putzas, D.; Rotter, H. W.;
Bordwell, F. G.; Satisch, A. V.; J i, G. Z.; Peters, E. M.; Peters, K.; v.
Schnering, H. G.; Walz, L. Liebigs Ann. 1996, 1055.
(2) (a) Pietzonka, T.; Seebach, D. Chem. Ber. 1991, 124, 1837. (b)
Pietzonka, T.; Seebach, D. Angew. Chem., Int. Ed. Engl. 1992, 31, 1481.
(c) Pietzonka, T.; Seebach, D. Angew. Chem., Int. Ed. Engl. 1993, 32,
716.
(5) Armstrong, D. R.; Davidson, M. G.; Moncrieff, D. Angew. Chem.,
Int. Ed. Engl 1995, 34, 478. For theoretical investigations about
lithiated ylides, see: Albright, T. A.; Schweizer, E. E. J . Org. Chem.
1976, 41, 1168.
(6) Alder, R. W.; Bowman, P. S.; Steele, W. R. S.; Winterman, D. R.
J . Chem. Soc., Chem. Commun. 1968, 723.
(7) (a) Oediger, H.; Mo¨ller, F.; Eiter, K.Synthesis 1972, 591. (b)
Schwesinger, R. Angew. Chem., Int. Ed. Engl. 1987, 26, 1164. (c) Reed,
R.; Re´au, R.; Dahan, F.; Bertrand, G. Angew. Chem., Int. Ed. Engl.
1993, 32, 399.
(8) (a) Lensink, C.; Xi, S. K.; Daniels, L. M.; Verkade, J . G. J . Am.
Chem. Soc. 1989, 111, 3478. (b) Laramay, M. A. H.; Verkade, J . G. J .
Am. Chem. Soc. 1990, 112, 9421. (c) Verkade, J . G. U. S. Patent
5051533, 1991. (d) Tang, J . S.; Dopke, J .; Verkade, J . G. J . Am. Chem.
Soc. 1993, 115, 5015. (e) Mohan, T.; Arumungam, S.; Wang, T.;
J acobson, R. A.; Verkade, J . G. Heteroatom Chem. 1996, 7, 455. (f)
Tang, J . S.; Verkade, J . G. Tetrahedron Lett. 1993, 34, 2903.
(3) J ohnson, A. W. (with special contributions by Kaska, W. C.;
Starzewski, K. A. O.; Dixon D. A.) In Ylides and Imines of Phosphorus;
Wiley & Sons: New York, 1993; pp 57 and 169.
(4) Bertrand, G.; Bigg, D.; Cazaux, J . B.; Goumri, S.; Guerret, O.
European Demand 97401142.1, 1997.
10.1021/jo9822030 CCC: $18.00 © 1999 American Chemical Society
Published on Web 04/30/1999

3742 J . Org. Chem., Vol. 64, No. 10, 1999
Notes
Sch em e 3
In all of the reactions mentioned above, no trace of
adducts resulting from the nucleophilic behavior of 2 has
been observed.
Su p p or ted Ylid es. To make more attractive the use
of ylides as strong nonnucleophilic bases, we investigated
the possibility of immobilizing an ylide on resins. Inter-
estingly, polymers of type A have been reported in the
literature11 and have been used as very efficient Wittig’s
reagents. Considering the relative acidity of the benzyl
and methyl protons, thermodynamic considerations sug-
gest that the ylide B should be preferred over A.3
However, it has been clearly demonstrated that the
polymers react in Wittig reactions as A, which strongly
suggest that the ylide carbon in B is nonnucleophilic,
because of the steric bulk of the polymer skeleton.
Therefore, in the hope of preparing a strongly hindered
nonnucleophilic supported base 3, a suspension of Mer-
ryfield’s resin and phosphine 4 in DCE was first stirred
under reflux for 5 days. After treatment, an elemental
analysis showed that 1.25 mequiv/g of phosphine was
grafted on the polymer. Then, deprotonation of the
phosphonium salt 3H+,Cl- with excess n-BuLi led to the
desired supported ylide 3 (Scheme 5).
Sch em e 4
To check the reactivity of 3, N-benzylation of 7a was
carried out, and the result was comparable to that
obtained with 2. Simple filtration of the solution afforded
7d , while the resin 3 could be regenerated by washing
with acetonitrile and simple deprotonation.
Con clu sion
These results show that the ylide 2 is a nonnucleophilic
strong base, comparable but cheaper than P4-t-Bu. Ap-
plications of the resin 3 in combinatorial synthesis are
currently being investigated.
Exp er im en ta l Section
All experiments were performed under an atmosphere of dry
argon or nitrogen. Conventional glassware was used. Compound
5 was prepared according to literature procedure.8a,f
2H+I-. To a diethoxymethane (DEM) solution (40 mL) of 4 (5
mL, 23 mmol) was added at room temperature an excess (4.69
g, 27.6 mmol) of 2-iodopropane. The solution was stirred under
reflux for 72 h. A white precipitate was formed, and after
filtration and recrystallization in acetonitrile, 2H+I- was ob-
tained as a white solid (6.97 g, 91% yield): mp 309 °C dec; 31P
2H+,X- (X ) Br or I) can be precipitated from the reaction
mixture by addition of ether, and, thus, easily eliminated
by simple filtration.
We then investigated several C-functionalization reac-
tions using 2 as a base (Scheme 4). With 1,4-benzodiaz-
epines, the results are very similar to those obtained with
LDA as the base.9 It is known that all benzodiazepines
are chiral by virtue of their nonplanarity.10 The introduc-
tion of a substituent at C3 only occurred on the less
sterically hindered face leading to only one diastereomer.
This has been confirmed by a single-crystal X-ray dif-
fraction study of 7k .
C-Alkylation reactions of the lactam 6e and succinim-
ide 8a have also been performed and led to the desired
products 6f and 8b, respectively. However, in the case
of 6f, heating during the step of deprotonation was
necessary to reach a reasonable yield (Scheme 4).
1
NMR (32 MHz, CD3CN) δ 65.0; H NMR (200 MHz, CD3CN) δ
3
3
3
1.31 (dd, J (HH) ) 7.1 Hz, J (PH) ) 18.2 Hz, 6H), 2.81 (d, J (PH)
)
2
3
9.4 Hz, 18H), 3.67 (sept d, J (PH) ) 9.8 Hz, J (HH) ) 7.1 Hz, 1H);
13C NMR (200 MHz, CD3CN) δ 15.13 (d, J (PC) ) 3.4 Hz), 23.80
2
1
2
(d, J (PC) ) 103.6 Hz), 36.43 (d, J (PC) ) 2.6 Hz). Anal. Calcd for
C9H25IN3P: C, 32.44; H, 7.56; N, 12.61. Found: C, 32.22; H, 7.40;
N, 12.41.
2. Potassium hydride (0.288 g, 7.2 mmol) was added at 0 °C
to a suspension of 2H+I- (2 g, 6 mmol) in 40 mL of THF. The
solution was stirred at room temperature until complete evolu-
tion of hydrogen (12 h). The solution was filtered, and after
evaporation of the solvent under vacuum, the residue was twice
extracted with 20 mL of pentane. Evaporation of pentane led to
2 as a colorless oil (0.92 g, 75% yield): 31P NMR (32 MHz, C6D6)
3
δ 60.6; 1H NMR (200 MHz, C6D6) δ 1.78 (d, J (PH) ) 15.7 Hz,
3
6H), 2.45 (d, J (PH) ) 9.3 Hz, 18H); 13C NMR (250 MHz, CDCl3)
1
2
δ 12.39 (d, J (PC) ) 221.0 Hz), 19.49 (d, J (PC) ) 15.9 Hz), 38.52
(d, 2J (PC) ) 2.8 Hz). Anal. Calcd for C9H24N3P: C, 52.66; H, 11.78;
N, 20.47. Found: C, 52.30; H, 11.52; N, 20.31. If 2 was complexed
with 1 equiv of LiI, the following values should be obtained: C,
31.88; H, 7.13; N, 12.39.
(9) Reitter, B. E.; Sachdeva, Y. P.; Wolfe, J . F.J . Org. Chem. 1981,
46, 3945.
(10) (a) Sikirica, M.; Vickovic, I. Cryst. Struct. Commun. 1982, 11,
1293. (b) Decorte, E.; Toso, R.; Fajdiga, T.; Comisso, G.; Moimas, F.;
Sega, A.; Sunjic, V.; Lisini, A. J . Heterocycl. Chem. 1983, 20, 1321. (c)
Simonyi, M.; Maksay, G.; Kovacs, I.; Tegyey, Z.; Parkanyi, L.; Kalman,
A.; O¨ tvo¨s, L. Bioorg. Chem. 1990, 18, 1. (d) Gilman, N. W.; Rosen, P.;
Earley, J . V.; Cook, C.; Todaro, L. J . J . Am. Chem. Soc. 1990, 112,
3969.
(11) (a) Bernard, M.; Ford, W. T. J . Org. Chem. 1983, 48, 326. (b)
Bernard, M.; Ford, W. T.; Nelson, E. C. J . Org. Chem. 1983, 48, 3164.

Notes
J . Org. Chem., Vol. 64, No. 10, 1999 3743
Sch em e 5
Com p a r ison of th e Ba sicities of 1, 2, a n d 5. To a THF
P r oced u r e for th e C-F u n ction a liza tion of th e La cta m
6e, Su ccin im id e 8a , a n d Ben zod ia zep in es 7b-d . A solution
of 2 (1.23 g, 6 mmol) in THF (27 mL) was added at -78 °C to a
THF solution (23 mL) of 6e, 8a , or 7b-d (5 mmol). The solution
was stirred at room temperature for 1 h (except for 6e: 45 °C,
6 h), and then the alkyl halide (6 mmol) was added. The mixture
was stirred for an additional hour. The solution was separated
from the phosphonium salts by addition of ether (60 mL) and
filtration. After evaporation of the solvent, the residue was
purified by silica gel column chromatography.
suspension (1 mL) of 2H+,I- (50 mg, 0.15 mmol) in an NMR tube
was added 1 equiv of 1 in THF (150 µL, 1 M). The 31P NMR
spectrum was measured right after the addition and 1 h later.
Both spectra were identical and show the signals due to 1H+
(+13.4 and -22.9 ppm) and 2 (+60.6 ppm). The same spectrum
was obtained by reacting a stoichiometric amount or an excess
of 2 with 1H+ under the same experimental conditions.
Similar experiments have been performed to compare the
basicities of 2 and 5. When a solution of 2 was added to an
equimolar solution of 5H+, after 1 h, the signals of 5 (+119.9
ppm) and 2H+(+ 65.0 ppm) were observed.
6f: eluent, ether/methanol 95/5; yellow oil; 0.47 g, 50% yield;
1H NMR (250 MHz, CDCl3) δ 2.00 (m, 2H), 2.63 (m, 2H), 2.79
(s, 3H), 3.10 (m, 3H), 7.19 (m, 5H); 13C NMR (250 MHz, CDCl3)
δ 23.88 (s), 29.59 (s), 36.99 (s), 43.27 (s), 47.39 (s), 126.17, 128.28,
128.88 (s), 139.29 (s), 175.72 (s). Anal. Calcd for C12H15NO: C,
76.16; H, 7.99; N, 7.40. Found: C, 76.63; H, 8.15; N, 6.92.
8b: eluent, ether; yellow oil; 0.29 g, yield 45%; IR(CDCl3) 1696
P r oced u r e for N-F u n ction a liza tion of th e La cta m 6a
a n d Ben zod ia zep in e 7a . A solution of 2 (3.15 mmol) in THF
(17 mL) was added at -78 °C to a solution of 6a or 7a (3 mmol)
in THF (14 mL). The solution was stirred for 1 h, and then 3.15
mmol of alkyl halide was added. The mixture was stirred for 3
h at room temperature. The solution was separated from the
phosphonium salts by addition of ether (60 mL) and filtration.
After evaporation of the solvent, the residue was purified by
silica gel column chromatography to yield compounds 6b-d and
7b-d .
1
cm-1; H NMR see ref 13; 13C NMR (250 MHz, CDCl3) δ 16.53
(s), 30.10 (s), 34.55 (s), 36.20 (s), 176.45, 180.55 (s). Anal. Calcd
for C6H9NO2: C, 56.68; H, 7.13; N, 11.02. Found: C, 56.81; H,
7.22; N, 10.84.
7e:9 eluent, pentane/ether 50/50; orange solid; mp 115 °C; 1.03
g, yield 55%.
6b:12a eluent, ether/methanol 85/15; yellow oil; 0.20 g, 60%
yield.
7f: eluent, ether; white solid; mp 141 °C; 0.84 g, 42% yield;
1H NMR (250 MHz, CDCl3) δ 1.45 (s, 9H), 3.40 (s, 3H), 3.11 (dd,
1
6c: eluent, ether; yellow oil; 0.45 g, 71% yield; H NMR (250
3
2
2J (HH) ) 17.1 Hz, J (HH) ) 7.0 Hz, 1H), 3.39 (dd, J (HH) ) 17.1
MHz, CDCl3) δ 1,43 (s, 9H), 1.80 (m, 4H), 2.55 (m, 2H), 3.35 (m,
2H), 4.09 (s, 2H); 13C NMR (250 MHz, CDCl3) δ 20.44, 22.42 (s),
27.73 (s), 31.72 (s), 49.21, 49.90 (s), 82.49 (s), 168.59, 172.37 (s).
Anal. Calcd for C11H19NO3: C, 61.95; H, 8.98; N, 6.57. Found:
C, 62.15; H, 8.71; N, 6.48.
3
3
3
Hz, J (HH) ) 6.8 Hz, 1H), 4.07 (dd, J (HH) ) 7.0 Hz, J (HH) ) 6.8
Hz, 1H), 7.25-7.57 (m, 8H); 13C NMR (250 MHz, CDCl3) δ 28.12
(s), 35.21 (s), 37.91 (s), 60.56 (s), 80.59 (s), 122.83-130.36 (s),
131.52, 137.97, 139.40, 142.20 (s), 167.20, 169.70, 171.25 (s).
Anal. Calcd for C22H23ClN2O3: C, 66.24; H, 5.81; N, 7.02.
Found: C, 66.51; H, 5.62; N, 6.77.
6d :12b eluent, ether/methanol 30/70; yellow oil; 0.40 g, 70%
yield.
7g:9,10a eluent, ether; orange solid; mp 103 °C; 0.64 g, 43%
yield.
7b:9 eluent, ether; white solid; 0.65 g, 76% yield.
7c: eluent, THF/pentane 90/10; yellow solid; mp 181 °C; 0.85
1
g, 74% yield; IR (CDCl3) 1688, 1740 cm-1; H NMR (250 MHz,
7h : eluent, pentane/ether 50/50; yellow solid; mp 128 °C; 1.20
g, 48% yield; 1H NMR (250 MHz, CDCl3) δ 1.40 (s, 9H), 1.44 (s,
2
CDCl3) δ 1.41 (s, 9H), 3.80 (d, J (HH) ) 10.7 Hz, 1H), 4.21 (d,
2
3
2
2J (HH) ) 15.0 Hz, 1H), 4.45 (d, J (HH) ) 15.0 Hz, 1H), 4.85 (d,
9H), 3.14 (dd, J (HH) ) 16.9 Hz, J (HH) ) 6.8 Hz, 1H), 3.43 (dd,
2J (HH) ) 16.9 Hz, J (HH) ) 7.0 Hz, 1H), 4.15 (dd, J (HH) ) 7.0 Hz,
3J (HH) ) 6.8 Hz, 1H), 4.20 (d, 2J (HH) ) 17.1 Hz, 1H), 4.48 (d, 2J (HH)
) 17.1 Hz, 1H), 7.25-7.60 (m, 8H); 13C NMR (250 MHz, CDCl3)
δ 27.90, 28.06 (s), 37.82 (s), 50.81 (s), 60.33 (s), 80.61, 82.43 (s),
123.02-131.64 (s), 129.89, 130.60, 130.98, 138.08 (s), 167.39,
167.76, 170.92 (s). Anal. Calcd for C27H31ClN2O5: C, 64.99; H,
6.26; N, 5.61. Found: C, 64.58; H, 5.92; N, 5.41.
3
3
2J (HH) ) 10.7 Hz, 1H), 7.21-7.60 (m, 8H); 13C NMR (250 MHz,
CDCl3) δ 27.65 (s), 51.03 (s), 55.88 (s), 83.50 (s), 121.63-131.98
(s), 130.23, 130.64, 137.85, 140.56 (s), 168.30, 170.26, 170.58 (s).
Anal. Calcd for C21H21ClN2O3: C, 65.54; H, 5.50; N, 7.28.
Found: C, 65.41; H, 5.76; N, 7.09.
7d : eluent, ether; orange solid; mp 178 °C; 0.84 g, 78% yield;
IR (CDCl3) 1679 cm-1; MS m/z 361 (M + 1); 1H NMR (250 MHz,
2
2
7i: eluent: pentane/ether 50/50; yellow solid; mp 81 °C; 0.93
CDCl3) δ 3.80 (d, J (HH) ) 10.5 Hz, 1H), 4.68 (d, J (HH) ) 15.5
Hz, 1H), 4.96 (d, 2J (HH) ) 10.5 Hz, 1H), 5.64 (d, 2J (HH) ) 15.5 Hz,
1H), 7.30 (m, 13H); 13C NMR (250 MHz, CDCl3) δ 49.77 (s), 56.83
(s), 123.94-131.30 (s), 130.02, 131.93, 136.20, 138.04, 140.43 (s),
169.48, 169.50 (s). Anal. Calcd for C22H17ClN2O: C, 73.23; H,
4.75; N, 7.76. Found: C, 73.50; H, 5.01; N, 7.52.
g, 39% yield; 1H NMR (250 MHz, CDCl3) δ 1.41 (s, 9H), 3.72 (m,
2
2
3H), 4.40 (d, J (HH) ) 16.7 Hz, 1H), 4.52 (d, J (HH) ) 16.7 Hz,
1H), 7.20-7.58 (m, 13H); 13C NMR (250 MHz, CDCl3) δ 27.79
(s), 37.69 (s), 50.77 (s), 64.72 (s), 82.33 (s), 122.69-131.45 (s),
130.68, 131.10, 138.10, 138.91, 141.08 (s), 167.30, 167.47, 169.49
(s). Anal. Calcd for C28H27ClN2O3: C, 70.80; H, 5.73; N, 5.90.
Found: C, 71.22; H, 5.83; N, 5.49.
(12) (a) Nabeya, A.; Endo, T. J . Org. Chem. 1991, 56, 9, 3194.
Schneider, H. J .; Agrawal, K. P. Tetrahedron 1984, 40, 6, 1024. (b)
Diez, A.; Castello, J .; Forns, P.; Rubivalta, M.; Grierson, D. S.
Tetrahedron 1994, 50, 22, 6585.
(13) Yamamoto, T.; Igarashi, K.; Komiya, S.; Yamamoto, A. J . Am.
Chem. Soc. 1980, 102, 25, 7448.

3744 J . Org. Chem., Vol. 64, No. 10, 1999
Notes
7j: eluent, pentane/ether 50/50; white solid; mp 152 °C; 1.08
g, 54% yield; 1H NMR (250 MHz, CDCl3) δ 1.41 (s, 9H), 1.70 (d,
3J (HH) ) 6.4 Hz, 3H), 3.77 (q, 3J (HH) ) 6.4 Hz, 1H), 4.23 (d, 2J (HH)
P r oced u r e for th e P r ep a r a tion of th e Su p p or ted P h os-
p h on iu m Sa lt 3H+. A DCE solution (100 mL) of Merrifield’s
resin (10 g, 2% cross linked; approximately 1 mequiv/g) and
phosphine 4 (3.26 g, 20 mmol) was stirred under reflux for 5
days in order to optimize the functionalization of the resin. After
being cooled to room temperature, the polymer was washed
several times, first with dichloromethane and then with diethyl
ether. The resin 3H+ was dried under vacuum at 60 °C until it
reached a stationary weight. Elemental analyses were in good
agreement with a total functionalization of the polymer. Anal.
Found: P, 3.9; 1.25 mequiv/g.
2
) 17.2 Hz, 1H), 4.51 (d, J (HH) ) 17.2 Hz, 1H), 7.21-7.60 (m,
8H); 13C NMR (250 MHz, CDCl3) δ 17.16 (s), 27.81 (s), 50.65 (s),
58.46 (s), 82.25 (s), 122.29-131.37 (s), 129.41, 130.82, 138.04,
141.18 (s), 167.04, 167.59, 170.50 (s). Anal. Calcd for C22H23
-
ClN2O3: C, 66.24; H, 5.81; N, 7.02. Found: C, 66.62; H, 5.58; N,
6.63.
7k : eluent, ether/pentane 90/10; yellow solid; mp 87 °C; 0.86
g, 38% yield; 1H NMR (250 MHz, CDCl3) δ 3.65 (m, 2H), 3.87
2
2
(m, 1H), 4.68 (d, J (HH))15.3 Hz, 1H), 5.68 (d, J (HH) ) 15.3 Hz,
1H), 6.95-7.50 (m, 18H); 13C NMR (250 MHz, CDCl3) δ 37.95
(s), 49.95 (s), 65.27 (s), 123.92-131.24 (s); 129.43, 131.99, 136.27,
137.94, 138.99, 140.05 (s), 167.43, 169.05 (s). Anal. Calcd for
C29H23ClN2O: C, 77.24; H, 5.14; N, 6.21. Found: C, 77.49; H,
5.48; N, 5.93.
Syn th esis of 3. The deprotonation of 3H+ was performed
using the procedure described in the literature for A14 and the
supported ylide 3 directly used.
P r oced u r e for N-Ben zyla tion of 7a Usin g 3. A THF
solution (20 mL) of 7a (0.27 g, 1 mmol) was added to a THF
suspension of 3 (1.1 g), and the mixture was stirred at room
temperature for 1 h. Then, benzylbromide (0.22 g, 1.3 mmol)
was added to the suspension, which was stirred overnight.
Filtration and evaporation of the solvent under vacuum led to
7d in 97% yield.
7l: eluent. pentane/ether 50/50; yellow solid; mp 166 °C; 1.00
g, 42% yield; 1H NMR (250 MHz, CDCl3) δ 1.47 (s, 9H), 3,25
2
3
2
(dd, J (HH) ) 16.9 Hz, J (HH) ) 7.5 Hz, 1H), 3.43 (dd, J (HH)
)
)
3
3
3
16.9 Hz, J (HH) ) 6.5 Hz, 1H), 4.19 (dd, J (HH) ) 7.6 Hz, J (HH)
6.5 Hz, 1H), 4.75 (d, 2J (HH) ) 15.5 Hz, 1H), 5.60 (d, 2J (HH) ) 15.5
Hz, 1H), 6.97-7.43 (m, 13H); 13C NMR (250 MHz, CDCl3) δ 28.14
(s), 37.80 (s), 50.28 (s), 60.62 (s), 80.70 (s), 124.01-131.38 (s),
129.54, 132.11, 136.20, 137.90, 140.31 (s), 167.50, 169.02, 171.30
(s). Anal. Calcd for C28H27ClN2O3: C, 70.80; H, 5.73; N, 5.90.
Found: C, 71.15; H, 6.02; N, 5.41.
Ack n ow led gm en t. Thanks are due to Expansia S.
A., la Communaute´ de Travail des Pyre´ne´es, and the
CNRS for financial support of this work.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal and
intensity collection data, position and thermal parameters, and
interatomic distances and angles for derivative 7k . This
material is available free of charge via the Internet at
http://pubs.acs.org.
7m : eluent, pentane/ether 50/50; pink solid; mp 164 °C; 1.26
1
3
g, 67% yield; H NMR (250 MHz, CDCl3) δ 1.77 (d, J (HH) ) 6.4
3
2
Hz, 3H), 3.81 (q, J (HH) ) 6.4 Hz, 1H), 4.68 (d, J (HH) ) 15.5 Hz,
1H), 5.70 (d, 2J (HH) ) 15.5 Hz, 1H), 6.99-7.42 (m, 13H); 13C NMR
(250 MHz, CDCl3) δ 17.32 (s), 49.82 (s), 58.81 (s), 123.94-131.30
(s), 130.38, 131.07, 136.39, 137.93, 140.20 (s), 167.16, 170.35 (s).
Anal. Calcd for C23H19ClN2O: C, 73.69; H, 5.11; N, 7.47.
Found: C, 73.19; H, 5.75; N, 7.13.
J O9822030
(14) Heitz, W.; Mitchels, R. Angew. Chem., Int. Ed. Engl. 1972, 11,
298.