Short syntheses of 8-substituted 8′-[1-(1′-phenylthio)ferrocenyl]-1,1′-binaphthyls from Suzuki coupling reactions. A strategy for generating new chiral ligands and charge-transfer complexes

Article abstract of DOI:10.1016/S0022-328X(01)01141-X

8′-Iodo-8-[1-(1′-phenylthio)ferrocenyl]-1,1′-binaphthyl, a precursor of chiral phosphines, and 8′-(4-methylphenyl)-8-[1-(1′-phenylthio)ferrocenyl]-1,1′-binaphthyl, a model compound for the preparation of charge-transfer complexes were synthesized via Suzuki coupling reactions of ferrocenylboronic acids and 8-substituted 8′-iodo-1,1′-binaphthyls. Sequential substitution of 8,8′-diiodo-1,1′-binaphthyl provided a facile method of generating unsymmetrical 8,8′-disubstituted 1,1′-binaphthyls.

Full text of DOI:10.1016/S0022-328X(01)01141-X

Journal of Organometallic Chemistry 637–639 (2001) 832–836
www.elsevier.com/locate/jorganchem
Note
Short syntheses of 8-substituted
8%-[1-(1%-phenylthio)ferrocenyl]-1,1%-binaphthyls from Suzuki
coupling reactions. A strategy for generating new chiral ligands
and charge-transfer complexes
Duy H. Hua *, James W. McGill, Masato Ueda, Heidi A. Stephany
Department of Chemistry, Kansas State Uni6ersity, Manhattan, KS 66506, USA
Received 19 February 2001; received in revised form 11 June 2001; accepted 14 June 2001
Abstract
8%-Iodo-8-[1-(1%-phenylthio)ferrocenyl]-1,1%-binaphthyl, a precursor of chiral phosphines, and 8%-(4-methylphenyl)-8-[1-(1%-
phenylthio)ferrocenyl]-1,1%-binaphthyl, a model compound for the preparation of charge-transfer complexes were synthesized via
Suzuki coupling reactions of ferrocenylboronic acids and 8-substituted 8%-iodo-1,1%-binaphthyls. Sequential substitution of
8,8%-diiodo-1,1%-binaphthyl provided a facile method of generating unsymmetrical 8,8%-disubstituted 1,1%-binaphthyls. © 2001
Elsevier Science B.V. All rights reserved.
Keywords: Chiral phosphines; Charge-transfer complexes; Suzuki coupling; Unsymmetrical 8,8%-disubstituted 1,1%-binaphthyls
can be enantioselectively oxidized with titanium te-
traisopropoxide, (R,R)-diethyl tartrate, and cumene hy-
droperoxide (CHP) [5], and the resulting ferrocenyl
sulfoxide may facilitate the resolution of atropisomeric
(axially dissymmetric) binaphthyls, these studies were
undertaken.
1. Introduction
Despite a large number of chiral ferrocenyl deriva-
tives that have been designed and synthesized in asym-
metric catalysis and material sciences [1a,1b], no
8-ferrocenyl-1,1%-binaphthyls [1c,1d] (nonracemic or
racemic) have been reported. Our recent interest in
using enantiopure 8%-substituted 8-(diphenylphos-
phinyl)-1,1%-binaphthyls [2] in asymmetric intramolecu-
lar Heck reactions [2c,2d] prompted us to synthesize
chiral 8-(diphenylphosphino)-8%-[1-(1%-phenylthio)ferro-
cenyl]-1,1%-binaphthyl (1). Herein, we report the synthe-
ses of 8%-iodo-8-[1-(1%-phenylthio)ferrocenyl]-1,1%-bi-
naphthyl (2), a precursor of chiral phosphine 1, and
8%-(4-methylphenyl)-8-[1-(1%-phenylthio)ferrocenyl]-1,1%-
binaphthyl (3), a model compound for the preparation
of charge-transfer complexes [3] from Suzuki coupling
reactions [4] of ferrocenylboronic acids and 8-substi-
tuted 8%-iodo-1,1%-binaphthyls. Since ferrocenyl sulfides
2. Results and discussion
Our approach leading to 8-substituted 8%-ferrocenyl
1,1%-binaphthyls is based upon the Suzuki coupling of
8,8%-diiodo-1,1%-binaphthyl (4) [6] with 1%-substituted 1-
ferrocenylboronic acids. Successful replacements of the
iodo groups in 4 sequentially at C8 and C8% with
different substituents will provide a facile method for
the generation of various useful unsymmetrical 8,8%-dis-
ubstituted 1,1%-binaphthyls. Diiodide 4 is readily pre-
pared from a palladium-catalyzed Ullmann coupling
reaction [6a] of 1,8-diiodonaphthalene [6b]. 1%-Substi-
tuted 1-ferrocenylboronic acids can be prepared from a
selective sequential lithiation-sulfenylation and lithia-
* Corresponding author.
E-mail address: duy@ksu.edu (D.H. Hua).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01141-X

D.H. Hua et al. / Journal of Organometallic Chemistry 637–639 (2001) 832–836
833
and diiodide 4 (60% recovery). The perylene by-product
is a homo-coupling [6a] product from 4.
tion-boronylation of 1,1%-ferrocenyl ditelluride [7] or
1,1%-bis(tri-n-butylstannyl)ferrocene [8].
First, Suzuki coupling of boronic acid 8 with iodide
5, 0.1 equivalents of tetrakis(triphenylphosphine)-
palladium and three equivalents of sodium carbonate in
dioxane–water (1:1) at 100–120 °C for 4 days gave a
27% yield of coupling product 3 along with 5% recov-
ered iodide 5. Asymmetric oxidation [5] of sulfide 3
with one equivalent each of titanium tetraisopropoxide,
Suzuki coupling of diiodide 4 with p-tolylboronic
acid (derived from p-bromotoluene with tert-BuLi in
ether followed by trimethyl borate), a catalytic amount
of tetrakis(triphenylphosphine)palladium (0.05 equiva-
lents), and potassium carbonate in dioxane–water (3:1)
at 70 °C for 11 h provided monoiodide 5 (37% yield)
and biscoupling product 6 (37% yield), along with
diiodide 4 (18% recovery) (Scheme 1).
L
-(R,R)-diethyl tartrate (DET), and CHP in methylene
chloride and water at −25 °C gave sulfoxide (SR)-9R
and (SR)-9S. Based on previous studies [5], the stereo-
chemistry of 9 at sulfur should be the R-configuration.
The two diastereomers, 9R and 9S, were separated by
column chromatography, and the absolute configura-
tion at the axially dissymmetric carbons (C1,1% of the
naphthyl ring) remains to be determined by X-ray
crystallography [10].
Second, Suzuki coupling of boronic acid 8 with io-
dide 4, 0.1 equivalents of tetrakis(triphenylphos-
phine)palladium and three equivalents of potassium
phosphate in dioxane–water (3:1) at 70 °C for 4 days
afforded desired ferrocene 2 (38% yield) and perylene
(12% yield) along with starting diiodide 4 (44% recov-
ery). Under similar reaction conditions but using three
equivalents of sodium carbonate in toluene and water
(1:1) as solvents, we obtained products 2 and perylene
in a ratio of 1:2 along with 15% of recovered diiodide 4.
Hence, use of a stronger base (sodium carbonate) and
toluene as co-solvent increase the yield of the homo-
coupling perylene by-product. Fortunately, the above
three compounds are separable by silica gel column
chromatography with hexane–ether (19:1) as eluent.
It should be noted that compound 2 may be con-
verted to chiral phosphine 1 by the method reported by
Imamoto et al. [11] involving metallation with tert-
BuLi followed by reaction with dichlorophenylphos-
1,1%-Bis-(tri-n-butylstannyl)ferrocene (7) [8] was se-
lected as our starting material to prepare the unsym-
metrical disubstituted ferrocene 8. Hence, treatment of
7 with one equivalent of n-BuLi in THF at −78 °C for
30 min followed by diphenyl disulfide (−78 to 25 °C
for 1 h) gave an 89% yield of 1-(tri-n-butylstannyl)-1%-
(phenylthio)ferrocene. Subsequent treatment with n-
BuLi in THF at −78 °C for 30 min followed by
trimethyl borate [4a] provided a 74% yield of boronic
acid 8 after aqueous work-up (with 0.5 N HCl) (Scheme
2). Attempted coupling of 1-(tri-n-butylstannyl)-1%-
(phenylthio)ferrocene with diiodide 4 and 0.1 equiva-
lents of tetrakis(triphenylphosphine)palladium in
toluene at 90 °C for 24 h (the Stille coupling) [9]
provided only a small amount of perylene (25% yield)
and mainly starting stannylferrocene (85% recovery)
Scheme 1.
phine, displacement with L-menthol, complexation with
borane·THF, separation of the diastereomers, and re-
moval of the borane with diethylamine. The use of
3,5-dicyanophenylboronic acid instead of p-tolyl-
boronic acid in the synthesis of compound 3 may
provide the dicyano derivative, an intramolecular
charge-transfer complex. This work and the synthesis of
chiral 8-substituted 8%-(diphenylphosphino)-1,1%-binaph-
thyls from diiodide 4 will be reported in due course.
3. Conclusions
Couplings of 8,8%-diiodo-1,1%-binaphthyl (4) with p-
tolylboronic acid and 1%-(phenylthio)-1-ferrocenyl-
boronic acid (8) and of 8-iodo-8%-(p-tolyl)-1,1%-
binaphthyl (5) with 8, were successfully carried out.
Despite its moderate yield, the sequential substitution
of 8,8%-diiodo-1,1%-binaphthyl, as illustrated, should
Scheme 2.

834
D.H. Hua et al. / Journal of Organometallic Chemistry 637–639 (2001) 832–836
prove to be one of the shortest routes to produce chiral
unsymmetrical 8,8%-disubstituted 1,1%-binaphthyls.
cm−1): w 3050, 2917, 1555, 1513, 1494, 1359, 1194,
1182, 1021, 957, 813, 764. H-NMR: l 8.03 (d, J=8
1
Hz, 1H), 8.00 (d, J=8 Hz, 1H), 7.95 (d, J=8 Hz, 1H),
7.58–7.46 (m, 4H), 7.40 (d, J=7.2 Hz, 1H), 7.32 (d,
J=7.2 Hz, 1H), 7.19 (m, 2H), 6.93 (t, J=8 Hz, 1H),
6.62 (d, J=8 Hz, 1H, p-Tol ring), 6.41 (d, J=8 Hz,
1H, p-Tol ring), 6.33 (d, J=8 Hz, 1H, p-Tol ring), 6.08
(d, J=8 Hz, 1H, p-Tol ring), 1.99 (s, 3H, Me). 13C-
NMR: l 142.1, 141.7, 140.9, 139.1, 139.0, 134.8, 134.7,
134.1, 132.6, 132.2, 131.9, 131.0, 130.5, 129.7, 129.1,
128.9, 128.8, 128.4, 128.0, 126.5, 126.1, 126.0, 125.0,
124.9, 92.7, 20.9. CIMS; m/z: 471 [M+1]. Anal.
Found: C, 68.69; H, 4.33. Calc. for C27H19I: C, 68.95;
H, 4.07%.
4. Experimental
4.1. General comments
Nuclear magnetic resonance spectra were obtained at
1
400 MHz for H and 100 MHz for 13C in deuteriochlo-
roform and recorded in ppm. Infrared spectra are re-
ported in wavenumbers (cm−1) and recorded from a
Nicolet 320 FTIR. Mass spectra were taken from a
Hewlett–Packard 5890 Series II, GC–MS. FAB spectra
were taken by using Xe beam (8 kV) and m-nitrobenzyl
alcohol as matrix. n-Butyllithium, trimethyl borate,
diphenyl disulfide, tri-n-butyltin chloride, titanium te-
traisopropoxide, (R,R)-diethyl tartrate, CHP and te-
trakis(triphenylphosphine)palladium were purchased
from Aldrich Chem. Co. Davisil silica gel, grade 643
(200–425 mesh), was used for the flash column chro-
matographic separation, and thin-layer chromatogra-
phy on silica gel (0.25 mm thickness; purchased form
Aldrich Chem. Co.) was used for TLC analysis. THF
and Et2O were distilled over sodium and benzophenone
before use. Methylene chloride was distilled over CaH2
and toluene and p-dioxane were distilled over LiAlH4.
H2O was degassed before use.
4.4. 8,8%-Bis-(p-tolyl)-1,1%-binaphthyl (6)
M.p. 177–179 °C. IR (film, cm−1): w 3047, 2916,
1
1512, 1367, 1182, 832, 808, 786, 771, 607. H-NMR: l
7.55 (d, J=7 Hz, 2H), 7.50–7.45 (m, 4H), 7.35–7.30
(m, 2H), 7.28 (d, J=7 Hz, 2H), 7.02 (d, J=7 Hz, 2H),
6.50 (d, J=8 Hz, 2H, p-Tol ring), 6.27 (d, J=8 Hz,
2H, p-Tol ring), 6.17 (d, J=8 Hz, 2H, p-Tol ring), 6.08
(d, J=8 Hz, 2H, p-Tol ring), 2.05 (s, 6H, Me). 13C-
NMR: l 141.9, 140.7, 138.4, 134.7, 133.8, 131.3, 130.8,
130.5, 128.8, 128.2, 127.9, 126.0, 125.9, 125.7, 125.0,
124.6, 21.0. EIMS; m/z: 434 [M+]. Anal. Found: C,
93.72; H, 5.88. Calc. for C34H26: C, 93.97; H, 6.03%.
4.2. 8,8%-Diiodo-1,1%-binaphthyl (4) [6]
4.5. 1-(Tri-n-butylstannyl)-1%-(phenylthio)ferrocene
M.p. 122–125 °C. IR (film, cm−1): w 3051, 1553,
1492, 1358, 1331, 1194, 1141, 1019, 946, 816, 806, 763,
714, 640. H-NMR: l 8.23 (d, J=7 Hz, 2H), 7.95 (t,
To a cold (−78 °C) solution of 1.56 g (2.0 mmol) of
bis-stannane 7 in 20 ml of THF under Ar, was added
1.3 ml (2.0 mmol) of n-BuLi (1.6 M in hexanes). After
the reaction solution was stirred at −78 °C for 30 min,
a solution of 0.436 g (2.0 mmol) of diphenyl disulfide in
4 ml of THF was added via cannula, and the solution
was stirred at −78 °C for 1 h and 25 °C for 3 h. The
reaction solution was diluted with aqueous NH4Cl,
extracted three times with Et2O, and the combined
ether layer was washed with brine, dried (MgSO4),
concentrated, and column chromatographed on silica
gel using hexane as solvent to give 1.04 g (89% yield)
of 1-(tri-n-butylstannyl)-1%-(phenylthio)ferrocene. IR
(neat, cm−1): w 3070, 2955, 2934, 2851, 1582, 1477,
1
J=7 Hz, 4H), 7.48 (t, J=7 Hz, 2H), 7.32 (d, J=7 Hz,
2H), 7.11 (t, J=8 Hz, 2H). 13C-NMR: l 142.3, 139.7,
135.6, 133.4, 133.3, 130.1, 130.0, 126.6, 124.9, 93.9.
CIMS; m/z: 507 [M+1]. This compound has been
reported previously [6], although the 13C-NMR data
was not reported.
4.3. 8-Iodo-8%-(p-tolyl)-1,1%-binaphthyl (5). A general
procedure for the Suzuki coupling reactions
A solution of 0.20 g (0.40 mmol) of diiodide 4, 54 mg
(0.40 mmol) of p-tolylboronic acid, 0.11 g (0.80 mmol)
of K2CO3, and 23 mg (0.02 mmol) of Pd(PPh3)4 in 6 ml
of p-dioxane and 2 ml of H2O under Ar was heated at
70 °C for 11 h. The reaction solution was cooled,
diluted with 20 ml of aqueous NH4Cl, and extracted
three times with Et2O. The combined ether layer was
washed with brine, dried (MgSO4), concentrated, and
column chromatographed on silica gel using a gradient
mixture of hexane and toluene as solvent to give 70 mg
(37% yield) of 5, 64 mg (37% yield) of 6, and 36 mg
(18% recovery) of diiodide 4. Compound 5: IR (film,
1
1376, 1025, 828, 736, 689. H-NMR: l 7.16 (m, 2H,
PhS), 7.05 (m, 3H, PhS), 4.44 (bs, 2H, Cp), 4.34 (bs,
2H, Cp), 4.26 (bs, 2H, Cp), 4.09 (bs, 2H, Cp), 1.58 (m,
6H), 1.36 (sextet, J=8 Hz, 6H), 1.05 (t, J=8 Hz, 6H),
0.92 (t, J=8 Hz, 9H). CIMS; m/z: 584 [M+1], 583.
13C-NMR: l 141.0, 128.5 (2C), 125.7 (2C), 124.7, 76.0,
75.3, 74.9, 72.2, 70.5, 70.1, 29.2, 27.4, 13.7, 10.3. Anal.
Found: C, 57.44; H, 7.13. Calc. for C28H40FeSSn: C,
57.66; H, 6.91%.

D.H. Hua et al. / Journal of Organometallic Chemistry 637–639 (2001) 832–836
835
4.6. 1%-(Phenylthio)-1-ferrocenylboronic acid (8)
ported in Ref. [5b] was followed, and compounds 9R
and 9S were separated by silica gel column chromatog-
raphy using a gradient mixture of hexane and Et2O as
solvent. The stereochemistry at C1,1% has not been
determined and is tentatively assigned. Less polar iso-
mer; TLC: Rf=0.16 in hexane–ether=1:1. IR (film,
cm−1): w 3051, 2924, 2854, 1600, 1442, 1365, 1083, 1046
To a cold (−78 °C) solution of 0.60 g (1.0 mmol) of
1-(tri-n-butylstannyl)-1%-(phenylthio)ferrocene in 10 ml
of THF under Ar, was added 0.75 ml (1.2 mmol) of
n-BuLi (1.6 M in hexanes). After the reaction solution
was stirred at −78 °C for 30 min, a solution of 0.13 ml
(1.2 mmol) of trimethyl borate in 2 ml of THF was
added. The solution was stirred at −78 °C for 1 h and
25 °C for 1 h, diluted with 10 ml of 0.5 N HCl, and
stirred at 0 °C for 1 h. The mixture was extracted with
Et2O three times, and the combined ether layer was
washed with brined, dried (MgSO4), and concentrated.
The resulting mixture was triturated with cold hexane
twice, and the remaining yellow solids were dried under
vacuo to give 0.25 g (74% yield) of 8 (as a ferrocenyl-
boroxine; a trimeric boric anhydride). IR (film, cm−1):
w 3399 (broad s, OH), 3062 (CH), 1790, 1705, 1580,
1
(s, SO), 1022. H-NMR: l 7.90 (d, J=7 Hz, 1H), 7.69
(d, J=7 Hz, 1H), 7.61 (t, J=7 Hz, 2H), 7.54 (d, J=7
Hz, 1H), 7.46–7.34 (m, 5H), 7.32–7.24 (m, 6H), 6.97
(d, J=7 Hz, 1H), 6.34 (d, J=7.5 Hz, 1H, p-Tol), 6.23
(d, J=7.5 Hz, 1H, p-Tol), 6.09 (d, J=7.5 Hz, 1H,
p-Tol), 5.94 (d, J=7.5 Hz, 1H, p-Tol), 4.33 (bs, 1H,
Cp), 3.99 (bs, 1H, Cp), 3.96 (bs, 1H, Cp), 3.91 (bs, 1H,
Cp), 3.77 (bs, 1H, Cp), 3.56 (bs, 1H, Cp), 3.51 (bs, 1H,
Cp), 3.45 (bs, 1H, Cp), 2.03 (s, 3H, Me). Anal. Found:
C, 78.97; H, 5.23. Calc. for C43H32FeOS: C, 79.14; H,
4.94%.
1
1471, 1377; H-NMR: l 7.16 (m, 1H, Ph), 7.07 (m, 2H,
Ph), 6.97 (m, 2H, Ph), 4.79 (bs, 2H, Cp), 4.63 (bs, 2H,
Cp), 4.40 (bs, 2H, Cp), 4.33 (bs, 2H, Cp). 13C-NMR: l
132.0, 128.6, 125.9, 124.9, 75.9, 75.5, 74.6, 70.8, 69.6.
Anal. Found: C, 56.37; H, 4.61. Calc. for
C16H15BFeO2S: C, 56.85; H, 4.47%.
4.9. (aS)-8-(4-Methylphenyl)-8-[(SR)-1-(1%-phenyl-
sulfinyl)ferrocenyl]-1,1%-binaphthyl (9S)
The stereochemistry at C1,1% has not been determined
and is tentatively assigned. More polar isomer; TLC:
1
Rf=0.10 in hexane–ether=1:1. H-NMR: l 7.83 (d,
4.7. 8-(4-Methylphenyl)-8%-[1-(1%-phenylthio)ferrocenyl]-
1,1%-binaphthyl (3)
J=7 Hz, 1H), 7.68 (d, J=7 Hz, 1H), 7.59 (d, J=7 Hz,
2H), 7.53 (d, J=7 Hz, 1H), 7.47–7.33 (m, 5H), 7.32–
7.24 (m, 6H), 6.97 (d, J=7 Hz, 1H), 6.34 (d, J=7.5
Hz, 1H, p-Tol), 6.24 (d, J=7.5 Hz, 1H, p-Tol), 6.09 (d,
J=7.5 Hz, 1H, p-Tol), 5.94 (d, J=7.5 Hz, 1H, p-Tol),
4.21 (bs, 1H, Cp), 4.07 (bs, 1H, Cp), 3.96 (bs, 1H, Cp),
3.92 (bs, 1H, Cp), 3.76 (bs, 1H, Cp), 3.57 (bs, 1H, Cp),
3.47 (bs, 1H, Cp), 3.42 (bs, 1H, Cp), 2.03 (s, 3H, Me).
Anal. Found: C, 79.40; H, 5.19. Calc. for C43H32FeOS:
C, 79.14; H, 4.94%.
The sulfoxide, 9S, was oxidized with m-chloroper-
benzoic acid to give the corresponding sulfone which
1H-NMR spectrum is different from that of sulfoxide
9S, and IR spectrum of the sulfone shows absorptions
at 1315 and 1141 cm−1 indicating the asym. and sym.
stretching of the SO2 moiety.
A mixture of 22 mg (0.064 mmol) of ferrocene 8, 10
mg (0.021 mmol) of iodide 5, 2 mg (0.002 mmol) of
Pd(PPh3)4, and 22 mg (0.21 mmol) of Na2CO3 in 0.2 ml
of p-dioxane and 0.1 ml of H2O was stirred in a sealed
tube under Ar at 110–120 °C for 4 days. The mixture
was cooled to 25 °C, diluted with aqueous NH4Cl, and
extracted three times with Et2O. The combined ether
layers were washed with brine, dried (MgSO4), concen-
trated, and column chromatographed on silica gel using
a gradient mixture of hexane and ether as solvent to
give 3.5 mg (27% yield) of 3 and 0.5 mg (5% recovery)
of 5. Compound 3: IR (film, cm−1): w 3049, 2920, 1731,
1
1607, 1477, 1365, 1024. H-NMR: l 7.98 (d, J=7 Hz,
1H), 7.68 (d, J=8 Hz, 1H), 7.60 (d, J=7 Hz, 2H), 7.51
(d, J=7 Hz, 1H), 7.44–7.36 (m, 3H), 7.32–7.24 (m,
3H), 7.10 (m, 2H), 7.02–6.92 (m, 4H), 6.35 (d, J=7.5
Hz, 1H, p-Tol ring), 6.24 (d, J=7.5 Hz, 1H, p-Tol
ring), 6.09 (d, J=7.5 Hz, 1H, p-Tol ring), 5.95 (d,
J=7.5 Hz, 1H, p-Tol ring), 4.02 (bs, 1H, Cp), 3.99 (bs,
1H, Cp), 3.98 (bs, 1H, Cp), 3.92 (bs, 1H, Cp), 3.62 (bs,
1H, Cp), 3.36 (bs, 2H, Cp), 3.31 (bs, 1H, Cp), 2.03 (s,
3H, Me). Anal. Found: C, 80.86; H, 5.32. Calc. for
C43H32FeS: C, 81.12; H, 5.07%.
4.10. 8-Iodo-8%-[1-(1%-phenylthio)ferrocenyl]-1,1%-
binaphthyl (2)
A mixture of 82 mg (0.24 mmol) of ferrocene 8, 98
mg (0.19 mmol) of iodide 4, 30 mg (0.025 mmol) of
Pd(PPh3)4, and 0.16 g (0.73 mmol) of potassium phos-
phate in 1.5 ml of p-dioxane and 0.5 ml of H2O was
stirred under Ar at 70 °C for 4 days. The mixture was
cooled to 25 °C, diluted with aqueous NH4Cl, and
extracted three times with Et2O. The combined ether
layer was washed with brine, dried (MgSO4), concen-
trated, and column chromatographed on silica gel using
a gradient mixture of hexane and ether as solvent to
4.8. (aR)-8-(4-Methylphenyl)-8-[(SR)-1-(1%-phenyl-
sulfinyl)ferrocenyl]-1,1%-binaphthyl (9R)
A chiral oxidation reaction procedure as that re-

836
D.H. Hua et al. / Journal of Organometallic Chemistry 637–639 (2001) 832–836
(b) A. Togni, R.L. Halterman (Eds.), Metallocenes, Wiley, New
York, NY, 1998;
give 38 mg (29% yield) of 2 and 43 mg (44% recovery)
of 4 along with 6 mg (12% yield) of perylene. Com-
pound 2: IR (film, cm−1): w 3051, 2924, 1733 (w), 1580,
1556, 1477, 1438, 1359, 1193, 1024, 819. EIMS; m/z:
(c) For a recent review of 1,1%-binaphthyl in asymmetric catalysis
and new materials, see: L. Pu, Chem. Rev. 98 (1998) 2405;
(d) For 2,2%-binaphthalenediyl-substituted ferrocenes: B.M. Fox-
man, M. Rosenblum, Organometallics 12 (1993) 4805.
[2] (a) J.W. McGill, H.-S. Sin, T.X.C. Nguyen, Y. Chen, X. Huang,
P. Roach, K. Mijares, D.H. Hua, Chiral 8,8%-Disubstituted 1,1%-
Binaphthyls in Asymmetric Catalytic Palladium-Mediated Ring
Closure Reactions, 35th Midwest Regional Meeting of the
American Chemical Society, St. Louis, MO, USA, 25–28 Octo-
ber, Abstr. No. 56, 2000, p. 85;
1
672 [M+]. H-NMR: l 8.34 (dd, J=7.2, 1.6 Hz, 1H),
8.07 (dd, J=7.6, 1.6 Hz, 1H), 7.97 (dd, J=7.6, 1.6 Hz,
1H), 7.91 (dd, J=7.6, 1.6 Hz, 1H), 7.75 (dd, J=7.6,
1.6 Hz, 1H), 7.62 (dd, J=7.6, 1.6 Hz, 1H), 7.53 (t,
J=7.2 Hz, 1H), 7.46 (dd, J=7.6, 1.6 Hz, 1H), 7.27–
7.10 (m, 6H), 7.04–6.96 (m, 3H), 4.20–4.14 (m, 4H,
Cp), 3.89 (m, 1H, Cp), 3.85 (m, 1H, Cp), 3.56 (m, 1H,
Cp), 3.21 (m, 1H, Cp). 13C-NMR: l 142.0, 141.8, 141.0,
138.2, 135.5, 134.9, 134.8, 134.4, 133.9, 133.5, 132.1,
131.8, 130.0, 129.5, 129.0, 128.8 (2C), 126.1, 125.9 (2C),
125.0, 124.9 (2C), 124.7, 95.3, 92.7, 73.5 (Cp), 72.9
(Cp), 72.1 (Cp), 72.0 (Cp), 67.9 (Cp), 67.1 (Cp). Anal.
Found: C, 64.56; H, 3.91. Calc. for C36H25FeIS: C,
64.31; H, 3.75%.
(b) K. Fuji, M. Sakurai, T. Kinoshita, T. Kawabata, Tetrahe-
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Acknowledgements
We gratefully acknowledge financial support from
National Science Foundation (0078921), National Insti-
tutes of Health, National Cancer Institute (CA86842),
American Heart Association, Heartland Affiliate
(0051658Z, 9951177Z), NASA-BioServe Space Tech-
nologies (NAGW-1197), and Great Plains Diabetes Re-
search, Inc.
(b) N.M. Lagneau, Y. Chen, P.M. Robben, H.-S. Sin, K.
Takasu, J.-S. Chen, P.D. Robinson, D.H. Hua, Tetrahedron 54
(1998) 7301 (and references cited therein).
[6] (a) G. Dyker, J. Org. Chem. 58 (1993) 234;
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[7] A. Chieffi, J.V. Comasseto, V. Snieckus, Synlett 2 (2000) 269.
[8] M.E. Wright, Organometallics 9 (1990) 853.
[9] J.K. Stille, Pure Appl. Chem. 57 (1985) 1771.
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