Palladium-Catalyzed Cross-Coupling Reactions with Aryl Nonaflates: A Practical Alternative to Aryl Triflates

Full text of DOI:10.1021/jo971636k

J . Org. Chem. 1998, 63, 203-208
203
Sch em e 1
P a lla d iu m -Ca ta lyzed Cr oss-Cou p lin g
Rea ction s w ith Ar yl Non a fla tes: A
P r a ctica l Alter n a tive to Ar yl Tr ifla tes
Mario Rottla¨nder and Paul Knochel*
Fachbereich Chemie, Philipps-Universita¨t Marburg,
Hans-Meerwein-Strasse, D-35032 Marburg, Germany
Received September 3, 1997
pling reactions. Respectively, the new reagents 1 and 2
are synthetic equivalents of the synthons 3 and 4.
In tr od u ction
Cross-coupling reactions with aryl triflates (ArOSO2CF3)
have been extensively used in synthesis.1,2 The electron-
withdrawing ability of the CF3SO2 group seems to be
essential for a rapid insertion of palladium(0) to the C-O
bond of the aryl triflate. Due to the moderate reactivity
of aryl triflates and the high cost of the triflate function-
ality, aryl fluorosulfonates have been proposed as an
alternative to triflates.2 These sulfonates display similar
reactivities compared to aryl triflates and give excellent
results in various cross-coupling reactions. However, the
not broadly commercialized fluorosulfonate anhydride
((FSO2)2O; bp ) 50 °C) has a comparable toxicity to
phosgene3 and should be handled with care. Alterna-
tively, aryl fluoroalkanesulfonates (ArOSO2(CF2)nCF3)
are easily prepared using commercially available fluoro-
alkanesulfonic anhydrides or halides.4 Especially attrac-
tive are aryl nonaflates (ArONf ) ArOSO2(CF2)3CF3)
which are readily prepared5 and are stable to flash
column chromatography. Herein, we wish to show their
utility in palladium-catalyzed cross-coupling reactions
and their use for the preparation of new polyfunctional
arylzinc reagents such as 1 and 2 which are new
multicoupling reagents.6
Resu lts a n d Discu ssion
Aryl nonaflates 5 are readily prepared by the reaction
of phenols with commercially available CF3(CF2)3SO2F
(1.5 equiv)5 in the presence of triethylamine (1.5 equiv)
in ether at 0 °C to rt. The conversion is complete after a
reaction time of 12 h affording the pure aryl nonaflates
5a -e in 92-98% yield (Scheme 1).
The palladium-catalyzed cross-coupling reaction7 of the
aryl nonaflate 5e with 3-(trifluoromethyl)phenylzinc
bromide8 in the presence of palladium bis(dibenzylidene-
acetone)9 (Pd(dba)2; 1 mol %) and bis(diphenylphosphi-
no)ferrocene10 (dppf; 1 mol %, 60 °C, 5 h) furnishes
4-(ethoxycarbonyl)-3′-(trifluoromethyl)biphenyl (6a ) in
90% yield. Compared to the corresponding aryl triflates,
aryl nonaflates display a slightly higher reactivity. Thus,
the competitive reaction of an equimolar mixture of the
aryl nonaflate 5e and the corresponding triflate (ethyl
(4-triflyloxy)benzoate) with 4-chlorophenylzinc bromide
(2 mol % Pd(dba)2, 2 mol % dppf, 55 °C, 8 h) shows that
the nonaflate reacts ca. 1.4 times faster than the triflate.
A selective reaction of the iodoaryl nonaflates 5a -c is
possible using Pd(dba)2 (0.5-1 mol %) and tri-o-fu-
rylphosphine11 (tfp; 1-2 mol %) leading to the cross-
coupling products 6b-g under very mild conditions (25
°C, 0.25-5 h) and in excellent yields (88-96%; Scheme
2 and Table 1). Compared to similar cross-coupling
reactions performed with iodoaryl triflates,7e cleaner
reactions and higher yields are obtained with the iodoaryl
nonaflates 5a -c.
These zinc reagents possess both an electrophilic (C-
ONf bond) and a nucleophilic (carbon-zinc bond) function
and give a selective access to various polyfunctional
terphenyls by using palladium(0)-catalyzed cross-cou-
(7) (a) Negishi, E.; Valente, L. F.; Kobayashi, M. J . Am. Chem. Soc.
1980, 102, 3298. (b) Kobayashi, M.; Negishi, E. J . Org. Chem. 1980,
45, 5223. (c) Negishi, E. Acc. Chem. Res. 1982, 15, 340. (d) Tamaru,
Y.; Ochiai, H.; Nakamura, T.; Yoshida, Z. Tetrahedron Lett. 1986, 27,
955. (e) Rottla¨nder, M.; Palmer, N.; Knochel, P. Synlett 1996, 573.
(8) Klement, I.; Rottla¨nder, M.; Tucker, C. E.; Majid, T. N.; Knochel,
P.; Venegas, P.; Cahiez, G. Tetrahedron 1996, 52, 7201.
(9) (a) Takahashi, Y.; Ito, T.; Sakai, S.; Ishii, Y. J . Chem. Soc., Chem.
Commun. 1970, 1065. (b) Rettig, M. F.; Maitlis, P. M. Inorg. Synth.
1990, 9, 3053.
(10) (a) Hayashi, T.; Konishi, M.; Kobori, Y.; Kumada, M.; Higuchi,
T.; Hirotsu, K. J . Am. Chem. Soc. 1984, 106, 158. (b) Hayashi, T.;
Katsuro, Y.; Okamoto, Y.; Kumada, M. Tetrahedron Lett. 1981, 22,
4449. (c) Hayashi, T.; Fujiwa, T.; Okamoto, Y.; Katsuro, Y.; Kumada,
M. Synthesis 1981, 1001. (d) Hayashi, T.; Katsuro, Y.; Kumada, M.
Tetrahedron Lett. 1980, 21, 3915. (e) Hayashi, T.; Konishi, M.; Yokota,
K.; Kumada, M. Chem. Lett. 1980, 6, 767. (f) Hayashi, T.; Konishi, M.;
Yokota, K.-I.; Kumada, M. J . Organomet. Chem. 1985, 285, 359. (g)
The phosphine dppf is conveniently prepared in high yield by using
the procedure of Brandsma: de Lang, R.-J .; van Soolingen, J .;
Verkruijsse, H. D.; Brandsma, L. Synth. Commun. 1995, 25, 2989.
(11) (a) Farina, V.; Krishnan, B. J . Am. Chem. Soc. 1991, 113, 9585.
(b) Farina, V.; Kapadia, S.; Krishnan, B.; Wang, C.; Liebeskind, L. S.
J . Org. Chem. 1994, 59, 5905.
(1) For an excellent review, see: (a) Ritter, K. Synthesis 1993, 735.
(b) Stang, P. J .; Hanack, M.; Subramanian, L. R. Synthesis 1982, 85.
(2) (a) Roth, G. P.; Fuller, C. E. J . Org. Chem. 1991, 56, 3493. (b)
Roth, G. P.; Sapino, C. Tetrahedron Lett. 1991, 32, 4073. (c) Roth, G.
P.; Thomas, J . A. Tetrahedron Lett. 1992, 33, 1959. (d) Lipshutz, B.
H.; Bugess-Henry, J .; Roth, G. P. Tetrahedron Lett. 1993, 34, 995.
(3) Muetterties, E. L.; Coffman, D. D. J . Am. Chem. Soc. 1958, 80,
5914.
(4) For the use of triflates and aryl fluoroalkanesulfonates in Heck
reactions, see: (a) Chen, Q.-Y.; Yang, Z.-Y. Tetrahedron Lett. 1986,
27, 1171. (b) de Meijere, A.; Meyer, F. E. Angew. Chem. 1994, 106,
2473. (c) Bra¨se, S.; de Meijere, A. In Palladium-Catalyzed Coupling
of Organyl Halides to Alkenes - The Heck Reaction; Stang, P. J .,
Diederich, F., Eds.; Wiley-VCH: Weinheim, 1997. (d) Webel, M.;
Reissig, H.-U. Synlett 1997, 1141.
(5) (a) Subramanian, L. R.; Bentz, H.; Hanack, M. Synthesis 1973,
293. (b) Niederpru¨m, H.; Voss, P.; Beyl, V. Liebigs. Ann. Chem. 1973,
20.
(6) For the recent preparation of benzylzinc multicoupling reagents,
see: Rottla¨nder, M.; Knochel, P. Tetrahedron Lett. 1997, 38, 1749.
S0022-3263(97)01636-8 CCC: $15.00 © 1998 American Chemical Society
Published on Web 01/09/1998

204 J . Org. Chem., Vol. 63, No. 1, 1998
Notes
Ta ble 1. Bip h en yl Non a fla tes 6b-g Obta in ed by
P a lla d iu m -Ca ta lyzed Cr oss-Cou p lin g Rea ction s betw een
Sch em e 2
Ar ylzin c Rea gen ts a n d Iod op h en yl Non a fla tes 5a -c
Sch em e 3
The biphenyl nonaflates 6c-g can be employed in a
second step to react with a different arylzinc bromide or
benzylzinc bromide12 using now a reaction temperature
of 55-60 °C and dppf as phosphine ligand. Under these
conditions, the nonaflate function is smoothly substituted
leading to the polyfunctional aromatic compounds 7a -i
in 87-96% isolated yields (55-60 °C, 1.5-36 h; Scheme
3 and Table 2).
The representative examples contained in Table 2 show
that ortho-, meta-, and para-substituted aryl nonaflates
undergo the cross-coupling reaction equally well with
uniformly high yields. Various functional groups can be
present either in the organozinc reagent or in the aryl
or heteroaryl nonaflate. Most coupling reactions are
complete within 20 h at 60 °C; however, ortho-substituted
aryl nonaflates require longer reaction times (36 h).
In the following, we wish to report the preparation of
new arylzinc reagents bearing an electrophilic nonaflate
function. Aryl iodides can be converted to nucleophilic
reagents by the insertion of zinc dust leading to arylzinc
iodides.13 Whereas iodophenyl triflates react with zinc
dust13 to the corresponding zinc reagent with modest
yield, the iodoaryl nonaflates 5a ,b undergo a clean
insertion of zinc dust previously activated14 with 1,2-
dibromoethane and Me3SiCl in N,N-dimethylacetamide
(DMAC) at 45 °C (7 h) leading to the desired zinc
reagents 1 and 2 in ca. 80% yield as estimated by
iodolysis experiments (GC analysis). These new orga-
nozincs undergo smooth cross-coupling reactions with
various functionalized aryl iodides in the presence of
Pd(dba)2 (1-2 mol %) and tfp (2-4 mol %) leading to the
polyfunctional biphenyl nonaflates 8 and 9 in 83-86%
yield (Scheme 4).
Interestingly, aryl nonaflates are also excellent sub-
strates for the performance of Stille and Suzuki cross-
coupling reactions. Thus, the treatment of the nonaflate
5e with the boronic acid 10 or the arylstannane 11
provides, under typical conditions for Suzuki15 or Stille16
coupling, the expected products 12 and 13 in 82-89%
yield (Scheme 5).
a
In summary, we have demonstrated that readily avail-
able aryl nonaflates are convenient substrates for the
Isolated yield of analytically pure product.
performance of palladium-catalyzed cross-coupling reac-
tions with organozinc halides. New arylzinc reagents
such as 1 and 2 bearing an electrophilic nonaflate
function have also been prepared and used for the
selective formation of cross-coupling products. The ef-
ficient preparation and purification of aryl nonaflates as
well as their very clean palladium-catalyzed cross-
coupling with organozincs and other organometallics
(12) Berk, S. C.; Yeh, M. C. P.; J eong, N.; Knochel, P. Organome-
tallics 1990, 9, 3053.
(13) Knochel, P.; Singer, R. D. Chem. Rev. (Washington, D.C.) 1993,
93, 2117.
(14) Knochel, P.; Yeh, M. C. P.; Berk, S. C.; Talbert, J . J . Org. Chem.
1988, 53, 2390.
(15) Oh-e, T.; Miyaura, N.; Suzuki, A. Synlett 1990, 221.
(16) Echavarren, A. M.; Stille, J . K. J . Am. Chem. Soc. 1987, 109,
5478.

Notes
J . Org. Chem., Vol. 63, No. 1, 1998 205
Ta ble 2. Ter p h en yls 7a -I Obta in ed by P a lla d iu m -ca ta lyzed Cr oss-Cou p lin g Rea ction s betw een Ar yl- or Ben zylzin c
Rea gen ts a n d F u n ction a lized Bip h en yl Non a fla tes 6c-g
a
Isolated yield of analytically pure product.
hexane or THF solutions (ca. 0.8 M) which were directly used
for the cross-coupling reactions.
should make these phenol derivatives an excellent alter-
native to aryl triflates.
Typ ica l P r oced u r e A: Zin c In ser tion in to a Non a fla te-
F u n ction a lized Ar yl Iod id e. P r ep a r a tion of 4-[(Non a flu o-
r obu ta n esu lfon yl)oxy]p h en ylzin c Iod id e (1). A dried and
argon-flushed 25-mL three-necked flask with a dropping funnel
and a thermometer was charged with zinc dust (1.95 g, 30 mmol),
DMAC (2 mL), and 1,2-dibromoethane (570 mg, 3.0 mmol). The
mixture was heated twice for 3 min to ca. 80 °C with the aid of
a heat gun. After the mixture cooled to rt, chlorotrimethylsilane
(0.45 mL, 3.6 mmol) was added, and the mixture was again
heated to ca. 80 °C as above. The dropping funnel was charged
with the nonaflate 5a (6.03 g, 12 mmol) in DMAC (8 mL). After
dropwise addition at 40-43 °C, the mixture was heated at 45
°C for 7 h resulting in a ready-to-use solution of 1 (10 mmol, ca.
83% yield, 0.85 M solution in DMAC as estimated by GC analysis
of a hydrolyzed and an iodolized aliquot).
Exp er im en ta l Section
Gen er a l. THF and DMAC were dried over sodium and CaH2,
respectively, and distilled prior to use. Commercially available
starting materials were used without further purification.
Melting points are uncorrected.
Sta r tin g Ma ter ia ls. The arylzinc reagents were prepared
from the corresponding aryl iodides or bromides via halogen-
lithium exchange followed by transmetalation according to a
literature procedure.8 Respectively, 2-cyanobenzylzinc bro-
mide,12 thiazol-2-ylzinc bromide,17 and N,N′-dibenzyluracil-5-
ylzinc iodide17 were prepared from the corresponding halides by
zinc insertion. All these preparation methods afforded THF/
3-[(Non aflu or obu tan esu lfon yl)oxy]ph en ylzin c Iodide (2).
This was prepared according to typical procedure A starting from
(17) Bhanu Prasad, A. S.; Stevenson, T. M.; Citineni, J . R.; Nyzam,
V.; Knochel, P. Tetrahedron 1997, 53, 7237.

206 J . Org. Chem., Vol. 63, No. 1, 1998
Notes
δ 7.86 (d, J ) 7.9 Hz, 1H), 7.38 (t, J ) 7.4 Hz, 1H), 7.30 (d, J )
8.1 Hz, 1H), 7.05 (t, J ) 7.8 Hz, 1H). 13C NMR (50 MHz,
CDCl3): δ 150.6, 140.9, 130.3, 129.6, 122.1, 120-105 (m), 89.3.
19F NMR (188 MHz, CDCl3): δ -81.4, -109.7, -121.3, -126.5.
MS (EI): 502 (59), 219 (100), 191 (23), 92 (93), 69 (29), 64 (35).
Anal. Calcd for C10H4F9IO3S: C, 23.92; H, 0.80. Found: C,
23.98; H, 1.08.
Sch em e 4
4-[(Tr iflu or om eth an esu lfon yl)oxy]ph en yl Non aflate (5d).
Starting from 4-[(trifluoromethanesulfonyl)oxy]phenol (1.95 g,
8.0 mmol), nonafluorobutanesulfonic fluoride (2.16 mL, 12
mmol), and triethylamine (1.68 mL, 12 mmol), the product 5d
was isolated after purification by flash chromatography (pen-
tane/ether, 97:3) as a white solid (4.11 g, 98%), mp 40-41 °C.
IR (KBr): 3123 (w), 1638 (m), 1616 (m), 1494 (m), 1426 (s), 1413
(s), 1250 (s), 1228 (s), 1143 (s), 906 (s), 619 (m) cm-1 1H NMR
.
(300 MHz, CDCl3): δ 7.40 (s, 4H). 13C NMR (75 MHz): δ 148.7,
148.5, 123.5, 118.7 (quart, J ) 321 Hz), 118-108 (m). 19F NMR
(188 MHz, CDCl3): δ -73.4, -81.4, -109.3, -121.5, -126.5. MS
(EI): 524 (14), 327 (15), 241 (29), 177 (27), 149 (13), 69 (100).
Anal. Calcd for C11H4F12O6S2: C, 25.20; H, 0.77. Found: C,
25.38; H, 0.80.
Eth yl 4-[(Non a flu or obu ta n esu lfon yl)oxy]ben zoa te (5e).
Starting from ethyl 4-hydroxybenzoate (3.32 g, 20 mmol),
nonafluorobutanesulfonic fluoride (5.4 mL, 30 mmol), and tri-
ethylamine (4.2 mL, 30 mmol), the product 5e was isolated after
purification by flash chromatography (pentane/ether, 95:5) as a
colorless liquid (8.36 g, 93%). IR (neat): 3077 (w), 2988 (w), 1727
(s), 1602 (m), 1498 (m), 1431 (s), 1279 (s), 1241 (s), 1205 (s), 1146
Sch em e 5
(s), 1018 (m), 894 (s), 861 (m), 774 (m) cm-1 1H NMR (200 MHz,
.
CDCl3): δ 8.13 (d, J ) 8.6 Hz, 2H), 7.34 (d, J ) 8.8 Hz, 2H),
4.38 (quart, J ) 7.2 Hz, 2H), 1.38 (t, J ) 7.2 Hz, 3H). 13C NMR
(50 MHz, CDCl3): δ 164.9, 152.7, 131.8, 130.7, 121.3, 120-108
(m), 61.5, 14.1. 19F NMR (188 MHz): δ -81.7, -109.6, -121.8,
-126.8. MS (EI): 448 (29), 420 (47), 403 (100), 356 (41), 339
(71), 165 (53), 109 (69), 92 (56), 69 (57). HRMS: calcd for
C
13H9F9O5S, 448.0026; found, 448.0027.
Typ ica l P r oced u r e B: Cr oss-Cou p lin g of a n Ar yl Non -
a fla te w ith a n Ar ylzin c Ha lid e in th e P r esen ce of a
P a lla d iu m (0) Ca ta lyst. P r ep a r a tion of 4-(Eth oxyca r bon -
yl)-3′-(tr iflu or om eth yl)bip h en yl (6a ). A dried and argon-
flushed 10-mL two-necked flask was charged with palladium
bis(dibenzylideneacetone)9 (5.8 mg, 0.01 mmol), bis(diphenylphos-
phino)ferrocene10 (5.5 mg, 0.01 mmol), and THF (1 mL). The
resulting solution was stirred for 10 min followed by the addition
of ethyl 4-[(nonafluorobutanesulfonyl)oxy]benzoate (5e; 448 mg,
1 mmol). After the mixture stirred for 5 min, 3-(trifluorometh-
yl)phenylzinc bromide (2.0 mL, 1.47 mmol, 0.74 M in THF) was
added, and the mixture was heated to 60 °C for 5 h. After usual
aqueous workup the crude product was purified by flash chro-
matography (pentane/ether, 95:5) yielding 6a as a white solid
(265 mg, 90%), mp 78 °C. IR (KBr): 3072 (w), 2984 (m), 1706
(s), 1611 (m), 1492 (m), 1441 (m), 1337 (s), 1310 (m), 1160 (m),
zinc dust (1.95 g, 30 mmol), 1,2-dibromoethane (570 mg, 3.0
mmol), chlorotrimethylsilane (0.45 mL, 3.6 mmol), and nonaflate
5b affording 2 (9.6 mmol, ca. 80% yield, 0.82 M in DMAC as
estimated by GC analysis of a hydrolyzed and an iodolized
aliquot).
The nonaflates 5 were prepared according to a literature
procedure.5
4-Iod op h en yl Non a fla te (5a ). Starting from 4-iodophenol
(8.64 g, 39.3 mmol), nonafluorobutanesulfonic fluoride (10.60 mL,
58.9 mmol), and triethylamine (8.25 mL, 58.9 mmol), the product
5a was isolated after purification by chromatography (pentane)
as a colorless liquid (18.6 g, 94%). IR (neat): 3072 (w), 3030
(w), 1478 (s), 1430 (s), 1241 (s), 1204 (s), 1181 (s), 1146 (s), 1009
(m), 890 (s), 828 (m), 731 (m) cm-1
.
1H NMR (200 MHz,
1128 (m), 1078 (m), 772 (s), 707 (s) cm-1 1H NMR (300 MHz,
.
CDCl3): δ 7.77 (d, J ) 11.7 Hz, 2H), 7.04 (d, J ) 11.9 Hz, 2H).
13C NMR (75 MHz, CDCl3): δ 149.8, 139.5, 123.3, 119.5-106.0
(m), 93.1. MS (EI): 502 (42), 219 (100), 191 (19), 92 (39), 64
(38). Anal. Calcd for C10H4F9IO3S: C, 23.92; H, 0.80. Found:
C, 23.93; H, 0.86.
CDCl3): δ 8.14 (d, J ) 8.5 Hz, 2H), 7.86 (s, 1H), 7.78 (d, J ) 7.5
Hz, 1H), 7.66-7.63 (m, 3H), 7.57 (t, J ) 7.7 Hz, 1H), 4.41 (quart,
J ) 7.2 Hz, 2H), 1.43 (t, J ) 7.1 Hz, 3H). 13C NMR (75 MHz,
CDCl3): δ 166.2, 143.9, 140.9, 131.4 (quart, J ) 32.5 Hz), 130.5,
130.2, 129.4, 127.1, 124.7 (quart, J ) 3.7 Hz), 124.1 (quart, J )
272.4 Hz), 124.0 (quart, J ) 3.8 Hz), 61.1, 14.3. MS (EI): 294
(47), 249 (100), 201 (11), 152 (16). HRMS: calcd for C16H13F3O2,
294.0866; found, 294.0868.
3-Iod op h en yl Non a fla te (5b). Starting from 3-iodophenol
(11.0 g, 50 mmol), nonafluorobutanesulfonic fluoride (13.5 mL,
75 mmol), and triethylamine (10.5 mL, 75 mmol), the product
5b was isolated after purification by chromatography (pentane)
as a colorless liquid (23.6 g, 94%). IR (neat): 3068 (w), 1587
(m), 1574 (m), 1464 (m), 1431 (s), 1240 (s), 1204 (s), 1146 (s),
4-Met h oxy-4′-[(n on a flu or ob u t a n esu lfon yl)oxy]b ip h en -
yl (6b). This was prepared according to typical procedure B
starting from iodide 5a (502 mg, 1 mmol), Pd(dba)2 (5.8 mg, 0.01
mmol), tfp (4.6 mg, 0.02 mmol), and 4-methoxyphenylzinc
bromide (1.20 mL, 1.15 mmol, 0.96 M in THF). Reaction time:
1.5 h at rt. After purification by flash chromatography (pentane/
ether, 98:2), the product 6b was obtained as a white solid (443.7
mg, 92%), mp 77-78 °C. IR (KBr): 3071 (w), 1638 (m), 1611
(m), 1495 (m), 1431 (m), 1355 (m), 1295 (m), 1238 (s), 1205 (s),
1035 (m), 895 (s), 785 (m) cm-1 1H NMR (200 MHz, CDCl3): δ
.
7.72 (d, J ) 8.2 Hz, 1H), 7.61 (m, 1H), 7.29-7.12 (m, 2H). 13C
NMR (75 MHz, CDCl3): δ 149.4, 137.6, 131.4, 130.4, 120.8,
119.5-106.2 (m), 93.8. 19F NMR (188 MHz, CDCl3): δ -81.2,
-109.3, -121.4, -126.4. MS (EI): 502 (55), 438 (18), 219 (44),
203 (24), 191 (26), 92 (100), 69 (37), 64 (33). Anal. Calcd for
C
10H4F9IO3S: C, 23.92; H, 0.80. Found: C, 23.90; H, 0.80.
2-Iod op h en yl Non a fla te (5c). Starting from 2-iodophenol
1148 (m), 1138 (m), 1038 (s), 892 (s), 824 (s) cm-1 1H NMR
.
(11.0 g, 50 mmol), nonafluorobutanesulfonic fluoride (13.5 mL,
75 mmol), and triethylamine (10.5 mL, 75 mmol), the product
5c was isolated after purification by chromatography (pentane)
as a colorless liquid (23.1 g, 92%). IR (neat): 3071 (w), 1572
(w), 1463 (s), 1430 (s), 1354 (s), 1238 (s), 1205 (s), 1144 (s), 1036
(200 MHz, CDCl3): δ 7.60 (d, J ) 9.0 Hz, 2H), 7.50 (d, J ) 9.0
Hz, 2H), 7.32 (d, J ) 9.0 Hz, 2H), 6.99 (d, J ) 9.0 Hz, 2H), 3.86
(s, 3H). 13C NMR (75 MHz, CDCl3): δ 159.8, 148.8, 141.3, 131.8,
128.3, 119-105 (m), 128.3, 128.3, 121.6, 114.5, 55.3. MS (EI):
482 (35), 199 (100). HRMS: calcd for C17H11F9O4S, 482.0216;
found, 482.0234.
(s), 1022 (s), 890 (s), 769 (s) cm-1 1H NMR (300 MHz, CDCl3):
.

Notes
4-[(Non a flu or obu ta n esu lfon yl)oxy]-3′-(tr iflu or om eth yl)-
J . Org. Chem., Vol. 63, No. 1, 1998 207
CDCl3): δ 7.47-7.40 (m, 8H). 13C NMR (75 MHz, CDCl3): δ
146.9, 134.6, 134.2, 131.8, 130.7, 129.4, 128.7, 128.6, 125.2
(quart, J ) 295 Hz), 122.1. MS (EI): 486 (44), 203 (79), 168
(100), 139 (21), 69 (16). Anal. Calcd for C16H8ClF9O3S: C, 39.48;
H, 1.66. Found: C, 39.41; H, 1.67.
bip h en yl (6c). This was prepared according to typical proce-
dure B starting from iodide 5a (3.01 g, 6 mmol), Pd(dba)2 (35
mg, 0.06 mmol), tfp (28 mg, 0.12 mmol), and 3-(trifluorometh-
yl)phenylzinc bromide (10.1 mL, 7.2 mmol, 0.71 M in THF).
Reaction time: 15 min at rt. After purification by flash
chromatography (pentane/ether, 98:2), the product 6c was
obtained as a colorless oil (2.91 g, 92%). IR (neat): 3078 (w),
1510 (m), 1486 (m), 1430 (s), 1337 (s), 1242 (s), 1206 (s), 1146
1-Ch lor o-3′′-(tr iflu or om eth yl)-4,1′:4′,1′′-ter p h en yl (7a ).
This was prepared according to typical procedure B starting from
nonaflate 6c (520 mg, 1 mmol), Pd(dba)2 (12 mg, 0.02 mmol),
dppf (11 mg, 0.02 mmol), and 4-chlorophenylzinc bromide (1.43
mL, 1.1 mmol). Reaction time: 1.5 h at 60 °C. After purification
by flash chromatography (pentane/ethyl acetate, 97:3), the
product 7a was obtained as a white solid (300 mg, 90%), mp
111-113 °C. IR (KBr): 1638 (m), 1616 (m), 1481 (m), 1341 (s),
(s), 1038 (m), 892 (s), 802 (s), 702 (m) cm-1 1H NMR (300 MHz,
.
CDCl3): δ 7.81 (s, 1H), 7.73 (d, J ) 7.7 Hz, 1H), 7.68-7.56 (m,
4H), 7.40 (d, J ) 8.7 Hz, 2H). 13C NMR (75 MHz, CDCl3): δ
149.8, 140.2, 140.2, 131.6 (quart, J ) 32.5 Hz), 130.5, 129.6,
129.0, 124.8 (quart, J ) 3.8 Hz), 124.1 (quart, J ) 272 Hz), 124.0
(quart, J ) 3.8 Hz), 122.0, 119-105 (m). MS (EI): 520 (19),
237 (100), 209 (23), 28 (32). Anal. Calcd for C17H8F12O3S: C,
39.24; H, 1.55. Found: C, 39.24; H, 1.65.
1187 (s), 1126 (s), 1099 (s), 1074 (m), 804 (s) cm-1
.
1H NMR
(300 MHz, CDCl3): δ 7.92 (s, 1H), 7.82 (d, J ) 7.7 Hz, 1H), 7.72-
7.57 (m, 8H), 7.46 (d, J ) 8.5 Hz, 2H). 13C NMR (75 MHz,
CDCl3): δ 141.2, 139.5, 138.8, 138.7, 133.7, 131.2 (quart, J )
32.1 Hz), 130.2, 129.3, 129.0, 128.2, 127.5, 127.4, 124.2 (quart,
J ) 272.4 Hz), 124.1 (quart, J ) 3.8 Hz), 123.7 (quart, J ) 3.8
Hz). MS (EI): 334 (30), 332 (100), 166 (11). HRMS: calcd for
4-(Th ia zol-2-yl)p h en yl Non a fla te (6d ). This was prepared
according to typical procedure B starting from iodide 5a (3.01
g, 6.0 mmol), Pd(dba)2 (35 mg, 0.06 mmol), tfp (28 mg, 0.12
mmol), and thiazol-2-ylzinc bromide (6.3 mL, 7.7 mmol, 1.22 M
in THF). Reaction time: 5 h at rt. After purification by flash
chromatography (pentane/ether, 95:5 to 90:10 gradient), the
product 6d was obtained as a pale yellow solid (2.58 g, 94%),
mp 50 °C. IR (KBr): 3089 (w), 3038 (w), 2849 (w), 1510 (m),
1479 (m), 1431 (s), 2251 (s), 1202 (s), 1146 (s), 896 (s), 846 (s),
C
19H12ClF3, 332.0574; found, 332.0580.
1-Cyan o-3′′-(tr iflu or om eth yl)-4,1′:4′,1′′-ter ph en yl (7b). This
was prepared according to typical procedure B starting from
nonaflate 6c (520 mg, 1 mmol), Pd(dba)2 (12 mg, 0.02 mmol),
dppf (11 mg, 0.02 mmol), and 4-cyanophenylzinc bromide (3.4
mL, 1.8 mmol, 0.55 M in THF). Reaction time: 5 h at 60 °C.
After purification by flash chromatography (pentane/ether, 95:5
to 90:10 gradient), the product 7b was obtained as a white solid
(305 mg, 94%), mp 96 °C. IR (KBr): 3069 (w), 2921 (w), 2223
(s), 1604 (m), 1484 (m), 1335 (s), 1268 (s), 1162 (s), 1128 (s), 1075
726 (s), 630 (s), 588 (s), 523 (s) cm-1
.
1H NMR (300 MHz,
CDCl3): δ 8.04 (d, J ) 8.8 Hz, 2H), 7.89 (d, J ) 3.2 Hz, 1H),
7.38-7.35 (m, 3H). 13C NMR (75 MHz, CDCl3): δ 166.0, 150.6,
144.2, 133.9, 128.4, 122.0, 119.8, 119-105 (m). 19F NMR (188
MHz, CDCl3): δ -81.5, -109.6, -121.8, -126.8. MS (EI): 459
(30), 176 (100), 148 (18), 69 (10), 58 (16), 28 (24). Anal. Calcd
for C13H6F9NO3S2: C, 34.00; H, 1.32; N, 3.05. Found: C, 34.21;
H, 1.32; N, 3.03.
(s), 823 (s), 802 (s), 701 (m) cm-1 1H NMR (300 MHz, CDCl3):
.
δ 7.88 (s, 1H), 7.82 (d, J ) 7.4 Hz, 1H), 7.79-7.57 (m, 10H). 13C
NMR (75 MHz, CDCl3): δ 144.8, 141.0, 140.0, 138.8, 132.7, 131.4
(quart, J ) 32.3 Hz), 130.3, 129.4, 127.9, 127.8, 127.6, 124.3
(quart, J ) 4.3 Hz), 124.1 (quart, J ) 272.2 Hz), 123.8 (quart, J
) 4.3 Hz), 118.8, 111.2. MS (EI): 323 (100), 161 (10). HRMS:
calcd for C20H12F3N, 323.0924; found, 323.0922.
3-[(Non a flu or obu ta n esu lfon yl)oxy]-3′-(tr iflu or om eth yl)-
bip h en yl (6e). This was prepared according to typical proce-
dure B starting from iodide 5b (4.0 g, 7.97 mmol), Pd(dba)2 (23
mg, 0.04 mmol), tfp (18 mg, 0.08 mmol), and 3-(trifluorometh-
yl)phenylzinc bromide (11.3 mL, 8.02 mmol, 0.71 M in THF).
Reaction time: 15 min at rt. After purification by flash
chromatography (pentane/ether, 98:2), the product 6e was
obtained as a colorless oil (3.77 g, 91%). IR (neat): 3077 (w),
1611 (m), 1429 (s), 1337 (s), 1242 (s), 1205 (s), 1134 (s), 922 (m),
4-(2-Cyan oben zyl)-3′-(tr iflu or om eth yl)biph en yl (7c). This
was prepared according to typical procedure B starting from
nonaflate 6c (520 mg, 1 mmol), Pd(dba)2 (12 mg, 0.02 mmol),
dppf (11 mg, 0.02 mmol), and 2-cyanobenzylzinc bromide (3.90
mL, 3 mmol, 0.77 M in THF). Reaction time: 24 h at 60 °C.
After purification by flash chromatography (pentane/ether, 95:
5), the product 7c was obtained as a colorless oil (314 mg, 93%).
IR (neat): 3032 (m), 2226 (m), 1599 (w), 1487 (m), 1445 (m),
791 (m), 699 (m) cm-1 1H NMR (300 MHz, CDCl3): δ 7.83 (s,
.
1H), 7.76 (d, J ) 7.7 Hz, 1H), 7.69 (d, J ) 7.8 Hz, 1H), 7.64-
7.51 (m, 4H), 7.38-7.32 (m, 1H). 13C NMR (75 MHz, CDCl3): δ
150.4, 142.6, 140.0, 131.8 (quart, J ) 32.6 Hz), 130.9, 130.6,
129.7, 127.2, 125.1 (quart, J ) 3.7 Hz), 124.1 (quart, J ) 274.3
Hz), 124.0 (quart, J ) 3.8 Hz), 121-105 (m), 120.7, 120.2. MS
(EI): 520 (45), 456 (15), 209 (100), 69 (25), 28 (10). HRMS: calcd
for C17H8F12O3S, 520.0000; found, 520.0002.
1337 (s), 1263 (s), 1165 (s), 1125 (s), 793 (s), 762 (s), 702 (s) cm-1
.
1H NMR (300 MHz, CDCl3): δ 7.84 (s, 1H), 7.74 (d, J ) 7.9 Hz,
1H), 7.56-7.50 (m, 10H), 4.27 (s, 2H). 13C NMR (75 MHz,
CDCl3): δ 144.4, 141.4, 138.7, 137.9, 132.9, 132.8, 130.5 (quart,
J ) 33.9 Hz), 130.1, 130.0, 129.5, 129.2, 127.3, 126.9, 124.2
(quart, J ) 272.4 Hz), 123.7 (quart, J ) 3.7 Hz), 123.5 (quart, J
) 3.8 Hz), 118.0, 112.5, 39.6. MS (EI): 337 (100), 116 (92).
HRMS: calcd for C21H14F3N, 337.1077; found, 337.1079.
4-(Th ia zol-2-yl)-3′-(tr iflu or om eth yl)bip h en yl (7d ). This
was prepared according to typical procedure B starting from
nonaflate 6d (459 mg, 1 mmol), Pd(dba)2 (12 mg, 0.02 mmol),
dppf (11 mg, 0.02 mmol), and 3-(trifluoromethyl)phenylzinc
bromide (3.9 mL, 2.8 mmol, 0.71 M in THF). Reaction time: 5
h at 55 °C. After purification by flash chromatography (pentane/
ethyl acetate, 95:5), the product 7d was obtained as a white solid
(278 mg, 91%), mp 120 °C. IR (KBr): 3234 (w), 1638 (m), 1616
(m), 1337 (s), 1264 (m), 1110 (s), 801 (m). 1H NMR (300 MHz,
CDCl3): δ 8.06 (d, J ) 8.3 Hz, 2H), 7.90-7.88 (m, 2H), 7.78 (d,
J ) 7.7 Hz, 1H), 7.67-7.62 (m, 3H), 7.55 (t, J ) 7.9 Hz, 1H),
7.34 (d, J ) 3.0 Hz, 1H). 13C NMR (50 MHz, CDCl3): δ 167.5,
143.8, 140.9, 140.8, 133.1, 131.2 (quart, J ) 32.2 Hz), 130.2,
129.3, 127.5, 127.0, 124.3 (quart, J ) 3.5 Hz), 124.1 (quart, J )
272.3 Hz), 123.6 (quart, J ) 4.0 Hz), 119.0. MS (EI): 305 (100),
58 (94). Anal. Calcd for C16H10F3NS: C, 62.94; H, 3.28; N, 4.59.
Found: C, 62.92; H, 2.98; N, 4.42.
3-(N,N′-Diben zylu r a cil-5-yl)p h en yl Non a fla te (6f). This
was made according to the preparation of 6a starting from iodide
5b (1.0 g, 2 mmol), Pd(dba)2 (12 mg, 0.02 mmol), tfp (8 mg, 0.04
mmol), and N,N′-dibenzyluracil-5-ylzinc iodide17 (3.6 mL, 2.5
mmol, 0.70 M in DMAC). Reaction time: 1.5 h at rt. After
purification by flash chromatography (pentane/ethyl acetate, 85:
15), the product 6f was obtained as a white foam (1.29 g, 96%).
IR (neat): 3067 (m), 3037 (m), 2963 (w), 1713 (s), 1651 (s), 1611
(m), 1495 (m), 1456 (s), 1354 (m), 1252 (s), 1148 (s), 1033 (m),
920 (s), 734 (s), 698 (m) cm-1
.
1H NMR (300 MHz, CDCl3): δ
7.57-7.55 (m, 3H), 7.46-7.17 (m, 12H), 5.24 (s, 2H), 4.96 (s,
2H). 13C NMR (75 MHz, CDCl3): δ 161.3, 150.9, 149.5, 140.4,
136.5, 135.4, 135.0, 129.8, 128.9, 128.4, 128.3, 127.8, 127.7, 127.6,
121.1, 120.1, 119-105 (m), 112.5, 52.4, 44.9. 19F NMR (188
MHz, CDCl3): δ -81.2, -109.4, -121.3, -126.3. MS (EI): 666
(31), 91 (100). HRMS: calcd for C28H19F9N2O5S, 666.0875;
found, 666.0871.
4-Ch lor o-2′-[(n on a flu or ob u t a n esu lfon yl)oxy]b ip h en yl
(6g). This was prepared according to typical procedure B
starting from iodide 5c (3.50 g, 6.97 mmol), Pd(dba)2 (23 mg,
0.04 mmol), tfp (18 mg, 0.08 mmol), and 4-chlorophenylzinc
bromide (11.4 mL, 8.8 mmol, 0.77 M in THF). Reaction time: 5
h at rt. After purification by flash chromatography (pentane/
ether, 95:5), the product 6g was obtained as a colorless oil (2.99
g, 88%). IR (neat): 3069 (w), 1475 (m), 1426 (s), 1240 (s), 1202
1-Ch lor o-3′′-(t r iflu or om et h yl)-4,1′:3′,1′′-t er p h en yl (7e).
This was prepared according to typical procedure B starting from
nonaflate 6e (520 mg, 1 mmol), Pd(dba)2 (12 mg, 0.02 mmol),
dppf (11 mg, 0.02 mmol), and 4-chlorophenylzinc bromide (1.55
mL, 1.2 mmol, 0.77 M in THF). Reaction time: 3 h at 60 °C.
After purification by flash chromatography (pentane/ether, 97:
3), the product 7e was obtained as a colorless oil. IR (neat):
(s), 1144 (s), 890 (m), 831 (m), 775 (m) cm-1 1H NMR (300 MHz,
.

208 J . Org. Chem., Vol. 63, No. 1, 1998
Notes
3038 (m), 1604 (m), 1493 (m), 1480 (m), 1338 (s), 1165 (s), 1126
4-Acet oxy-4′-[(n on a flu or ob u t a n esu lfon yl)oxy]b ip h en -
yl (8). This was prepared according to typical procedure B
starting from 4-iodophenyl acetate (524 mg, 2 mmol), Pd(dba)2
(12 mg, 0.02 mmol), tfp (9 mg, 0.04 mmol), and arylzinc iodide
1 (3.53 mL, 3.0 mmol, ca. 0.85 M in DMAC). Reaction time: 12
h at rt. After purification by flash chromatography (pentane/
ether, 95:5), the product 8 was obtained as a white solid (877
mg, 86%), mp 70 °C. IR (KBr): 3045 (m), 2980 (m), 1763 (m),
1637 (s), 1493 (m), 1227 (s), 1204 (s), 1144 (m), 701 (m), 687
(s), 788 (s), 702 (s) cm-1 1H NMR (300 MHz, CDCl3): δ 7.93 (s,
.
1H), 7.83 (d, J ) 7.7 Hz, 1H), 7.78 (s, 1H), 7.69 (d, J ) 7.7 Hz,
1H), 7.65-7.52 (m, 6H), 7.47 (d, J ) 8.5 Hz, 2H). 13C NMR (75
MHz, CDCl3): δ 141.8, 140.9, 140.5, 139.3, 133.8, 131.3 (quart,
J ) 32.4 Hz), 130.5, 129.6, 129.3, 129.0, 128.5, 126.7, 126.5,
125.9, 124.2 (quart, J ) 272.9 Hz), 124.2 (quart, J ) 3.7 Hz),
124.0 (quart, J ) 3.7 Hz). MS (EI): 332 (100). Anal. Calcd for
C19H12ClF3: C, 68.58; H, 3.63. Found: C, 68.35; H, 3.76.
(m), 660 (m) cm-1 1H NMR (300 MHz, CDCl3): δ 7.61 (d, J )
.
1-Cyan o-3′′-(tr iflu or om eth yl)-4,1′:3′,1′′-ter ph en yl (7f). This
was prepared according to typical procedure B starting from
nonaflate 6e (520 mg, 1 mmol), Pd(dba)2 (12 mg, 0.02 mmol),
dppf (11 mg, 0.02 mmol), and 4-cyanophenylzinc bromide (3 mL,
1.65 mmol, 0.55 M in THF). Reaction time: 12 h at 60 °C. After
purification by flash chromatography (pentane/ether, 95:5 to 88:
12 gradient), the product 7f was obtained as a pale yellow solid
(288 mg, 89%), mp 79-81 °C. IR (KBr): 3052 (w), 2230 (m),
1638 (m), 1607 (m), 1510 (m), 1483 (m), 1341 (s), 1241 (m), 1161
8.8 Hz, 2H), 7.56 (d, J ) 8.6 Hz, 2H),7.36 (d, J ) 8.8 Hz, 2H),
7.20 (d, J ) 8.6 Hz, 2H), 2.34 (s, 3H). 13C NMR (75 MHz,
CDCl3): δ 169.3, 150.7, 149.2, 140.7, 137.0, 128.8, 128.2, 122.1,
121.6, 119-105 (m), 21.0. MS (EI): 510 (5), 467 (25), 185 (100),
157 (15), 43 (25). Anal. Calcd for C18H11F9O5S: C, 42.36; H,
2.17. Found: C, 42.60; H, 2.21.
3-(Eth oxyca r bon yl)-3′-[(n on a flu or obu ta n esu lfon yl)oxy]-
bip h en yl (9). This was prepared according to typical procedure
B starting from ethyl 3-iodobenzoate (828 mg, 3 mmol), Pd(dba)2
(36 mg, 0.06 mmol), tfp (27 mg, 0.12 mmol), and arylzinc iodide
2 (4.39 mL, 3.6 mmol, ca. 0.82 M in DMAC). Reaction time:
0.5 h at rt. After purification by flash chromatography (pentane/
ether, 90:10), the product 9 was obtained as a colorless oil (1.30
g, 83%). IR (neat): 3065 (m), 2980 (m), 1720 (s), 1611 (m), 1574
(m), 1427 (s), 1298 (s), 1242 (s), 1202 (s), 1145 (s), 933 (s), 881
(s), 1122 (s), 1076 (m), 800 (s), 703 (m) cm-1 1H NMR (300 MHz,
.
CDCl3): δ 7.89 (s, 1H), 7.82 (d, J ) 7.7 Hz, 1H), 7.78 (s, 1H),
7.73 (s, 4H), 7.68-7.56 (m, 5H). 13C NMR (75 MHz, CDCl3): δ
145.2, 141.5, 140.7, 140.1, 132.7, 131.3 (quart, J ) 32.3 Hz),
130.5, 129.8, 129.4, 127.8, 127.5, 126.8, 126.1, 124.4 (quart, J )
3.7 Hz), 124.2 (quart, J ) 272.2 Hz), 124.0 (quart, J ) 3.7 Hz),
118.8, 111.3. MS (EI): 323 (100), 161 (10). Anal. Calcd for C20
-
(s), 797 (s), 754 (s) cm-1 1H NMR (200 MHz, CDCl3): δ 8.09 (s,
.
H12F3N: C, 74.30; H, 3.74; N, 4.33. Found: C, 74.17; H, 3.79;
N, 4.35.
1H), 7.95 (d, J ) 7.7 Hz, 1H), 7.57 (d, J ) 7.7 Hz, 1H), 7.51-
7.33 (m, 4H), 7.15 (d, J ) 8.2 Hz, 1H), 4.27 (quart, J ) 7.2 Hz,
2H), 1.27 (t, J ) 7.2 Hz, 3H). 13C NMR (50 MHz, CDCl3): δ
166.2, 150.3, 142.9, 139.2, 131.4, 130.7, 129.3, 129.1, 128.2, 127.1,
120.3, 120.1, 119-105 (m), 61.3, 14.2. 19F NMR (188 MHz,
CDCl3): δ -81.2, -109.5, -121.4, -126.4. MS (EI): 524 (100),
479 (30), 213 (74), 196 (27), 139 (22), 69 (20). Anal. Calcd for
3-(2-Cyan oben zyl)-3′-(tr iflu or om eth yl)biph en yl (7g). This
was prepared according to typical procedure B starting from
nonaflate 6e (520 mg, 1 mmol), Pd(dba)2 (12 mg, 0.02 mmol),
dppf (11 mg, 0.02 mmol), and 2-cyanobenzylzinc bromide (4.0
mL, 2.2 mmol, 0.55 M in THF). Reaction time: 20 h at 60 °C.
After purification by flash chromatography (pentane/ether, 95:5
to 90:10 gradient), the product 7g was obtained as a pale yellow
oil (293 mg, 87%). IR (neat): 3065 (m), 2224 (s), 1600 (m), 1486
(m), 1444 (m), 1337 (s), 1267 (m), 1165 (s), 1125 (s), 1075 (m),
C
19H13F9O5S: C, 43.52. H, 2.50. Found: C, 43.50; H, 2.49.
4-(Eth oxyca r bon yl)-3′-n itr obip h en yl (12). This was made
according to a literature procedure15 starting from nonaflate 5e
(448 mg, 1 mmol), Pd(dba)2 (12 mg, 0.02 mmol), dppf (11 mg,
0.02 mmol), K3PO4‚3H2O (400 mg, 1.5 mmol), and boronic acid
10 (184 mg, 1.1 mmol). Reaction time: 1 h at 80 °C in dioxane.
After recrystallization from MeOH, the product 12 was obtained
as a white solid (241 mg, 89%), mp 112-114 °C (lit.18 mp 113-
115 °C). 1H NMR (300 MHz, CDCl3): δ 8.45 (t, J ) 2.0 Hz, 1H),
8.25-8.21 (m, 1H), 8.15 (dt, J ) 8.7, 2.0 Hz, 2H), 7.96-7.91 (m,
1H), 7.69-7.64 (m, 3H), 4.41 (quart, J ) 7.1 Hz, 2H), 1.42 (t, J
) 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 166.0, 148.7, 142.7,
141.6, 133.0, 130.5, 130.3, 129.9, 127.0, 122.7, 122.0, 61.1, 14.3.
MS (EI): 271 (39), 243 (27), 226 (100), 152 (29).
762 (m), 703 (s) cm-1
.
1H NMR (300 MHz, CDCl3): δ 7.85 (s,
1H), 7.78 (d, J ) 7.7 Hz, 1H), 7.70-7.30 (m, 10H), 4.33 (s, 2H).
13C NMR (75 MHz, CDCl3): δ 144.4, 141.6, 140.1, 139.6, 132.9,
132.8, 130.0 (quart, J ) 32.1 Hz), 130.4, 129.9, 129.3, 129.2,
128.5, 127.7, 126.9, 125.5, 124.1 (quart, J ) 272.3 Hz), 124.0-
123.7 (m), 118.1, 112.5, 40.1. MS (EI): 337 (100). HRMS: calcd
for C21H14F3N, 337.1081; found, 337.1079.
3-(N,N′-Dib en zylu r a cil-5-yl)-4′-m et h oxyb ip h en yl (7h ).
This was prepared according to typical procedure B starting from
nonaflate 6f (890 mg, 1.3 mmol), Pd(dba)2 (15 mg, 0.03 mmol),
dppf (14 mg, 0.03 mmol), and 4-methoxyphenylzinc bromide (2.8
mL, 2.0 mmol, 0.71 M in THF). Reaction time: 4 h at 60 °C.
After purification by flash chromatography (pentane/ethyl ac-
etate, 80:20), the product 7h was obtained as a white solid (582
mg, 92%), mp 145 °C. IR (KBr): 3069 (w), 1708 (s), 1650 (s),
1515 (m), 1482 (m), 1451 (s), 1364 (m), 1250 (s), 1237 (s), 1177
4-(Eth oxyca r bon yl)bip h en yl (13). This was made accord-
ing to a literature procedure16 starting from nonaflate 5e (448
mg, 1 mmol), Pd(dba)2 (24 mg, 0.04 mmol), dppf (44 mg, 0.08
mmol), LiCl (240 mg, 6 mmol), and phenyltributyltin (11) (404
mg, 1.1 mmol). Reaction time: 12 h at 105 °C in DMF. After
purification by flash chromatography (pentane/ether, 90:10), the
product 13 was obtained as a white solid (185 mg, 82%), mp
48-49 °C (lit.18 mp 49.2-49.6 °C). 1H NMR (300 MHz, CDCl3):
δ 8.14 (d, J ) 8.4 Hz, 2H), 7.69-7.63 (m, 4H), 7.48-7.40 (m,
3H), 4.43 (quart, J ) 7.1 Hz, 2H), 1.44 (t, J ) 7.1 Hz, 3H). 13C
NMR (75 MHz, CDCl3): δ 166.4, 145.4, 139.9, 130.0, 129.2, 128.8,
128.0, 127.2, 126.9, 60.9, 14.3. MS (EI): 226 (100), 181 (80),
152 (47).
(m), 1022 (m), 804 (m), 728 (s) cm-1
.
1H NMR (300 MHz,
CDCl3): δ 7.67 (s, 1H), 7.50 (d, J ) 7.3 Hz, 2H), 7.56-7.48 (m,
3H), 7.40-7.31 (m, 11H), 6.98 (d, J ) 8.8 Hz, 2H), 5.27 (s, 2H),
4.97 (s, 2H), 3.84 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 161.8,
159.1, 151.2, 140.9, 139.5, 136.8, 135.3, 133.2, 129.1, 129.0, 128.6,
128.3, 128.3, 128.1, 127.9, 127.5, 126.7, 126.5, 126.2, 114.8, 114.1,
55.2, 52.3, 44.8. MS (EI): 474 (100), 91 (71). HRMS: calcd for
C31H26N2O3, 474.1939; found, 474.1943.
Ack n ow led gm en t. We thank the BASF AG (Lud-
wigshafen), the BMBF (03 D0056 2), and the DFG (SFB
260) for generous financial support. We also thank the
Bayer AG (Leverkusen) for the generous gift of chemi-
cals.
Su p p or tin g In for m a tion Ava ila ble: 1H and 13C NMR
spectra of compounds 5a -e, 6a -g, 7a -i, 8, 9, 12, and 13 and
19F NMR spectra of compounds 5d , 6f, and 9 (53 pages). This
material is contained in libraries on microfiche, immediately
follows this article in the microfilm version of the journal, and
can be ordered from the ACS; see any current masthead page
for ordering information.
4-Ch lor o-2′-(2-cya n oben zyl)bip h en yl (7i). This was pre-
pared according to typical procedure B starting from nonaflate
6g (487 mg, 1 mmol), Pd(dba)2 (12 mg, 0.02 mmol), dppf (11 mg,
0.02 mmol), and 2-cyanobenzylzinc bromide (4.0 mL, 2.4 mmol,
0.60 M in THF). Reaction time: 36 h at 60 °C. After purification
by flash chromatography (pentane/ether, 95:5), the product 7i
was obtained as a colorless oil (270 mg, 89%). IR (neat): 3064
(m), 2225 (s), 1599 (m), 1478 (s), 1447 (m), 1090 (s), 1007 (m),
834 (m), 760 (s) cm-1 1H NMR (300 MHz, CDCl3): δ 7.35 (dd,
.
J ) 7.7, 1.4 Hz, 1H), 7.42 (dt, J ) 7.6, 1.4 Hz, 1H), 7.37-7.21
(m, 5H), 7.19-7.12 (m, 3H), 6.96 (d, J ) 7.9 Hz, 1H), 4.18 (s,
2H). 13C NMR (75 MHz, CDCl3): δ 144.9, 141.3, 139.7, 136.1,
133.3, 132.8, 132.7, 130.5, 130.3, 130.0, 128.5, 127.0, 126.7, 117.8,
112.7, 37.6. MS (EI): 305 (34), 303 (100), 268 (18), 267 (33),
266 (11), 165 (15), 133 (14). HRMS: calcd for C20H14ClN,
303.0818; found, 303.0815.
J O971636K
(18) Berliner, E.; Liu, L. H. J . Am. Chem. Soc. 1953, 75, 2417.