Metallation reactions on 2,2′-bis(diphenylphosphinoyl)-1,1′-binaphthyl [BINAP(O)2]

Article abstract of DOI:10.1246/bcsj.76.1233

The behavior of BINAP(O)₂ upon treatment with lithium or magnesium amides under various conditions has been studied. With 2,2,6,6-tetramethylpiperidinomagnesium bromide, the ortho positions of opposed phenyl rings were selectively metallated, forming stable intermediates, while the use of lithium amides caused rearrangements with displacement of one diphenylphosphinoyl group and the formation of strained P-heterocycles (2, 5, 6) with unusual architectures. Monophosphine oxides 2 and 3a have been reduced to phosphines 13 and 14 in good yield, while substituted BINAP(O)₂ derivatives failed to give the desired diphosphines. The stereochemistry of six phosphine oxides (2, 3a, 5, 8, 9, 11a) and one phosphine (13) has been elucidated by crystal structure determinations.

Full text of DOI:10.1246/bcsj.76.1233

ꢀ 2003 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 76, 1233–1244 (2003) 1233
Metallation Reactions on 2,20-Bis(diphenylphosphinoyl)-1,10-binaphthyl
[BINAP(O)2]
ꢀ
Michael Widhalm and Kurt Mereitery
Institute of Organic Chemistry, University of Vienna, Wahringer Straße 38, A-1090 Vienna, Austria
¨
yInstitute of Chemical Technology and Analytics, Vienna University of Technology,
Getreidemarkt 9, A-1060 Vienna, Austria
(Received October 21, 2002)
The behavior of BINAP(O)2 upon treatment with lithium or magnesium amides under various conditions has been
studied. With 2,2,6,6-tetramethylpiperidinomagnesium bromide, the ortho positions of opposed phenyl rings were se-
lectively metallated, forming stable intermediates, while the use of lithium amides caused rearrangements with displace-
ment of one diphenylphosphinoyl group and the formation of strained P-heterocycles (2, 5, 6) with unusual architectures.
Monophosphine oxides 2 and 3a have been reduced to phosphines 13 and 14 in good yield, while substituted BINAP(O)2
derivatives failed to give the desired diphosphines. The stereochemistry of six phosphine oxides (2, 3a, 5, 8, 9, 11a) and
one phosphine (13) has been elucidated by crystal structure determinations.
Among the plenitude of chiral ligands already developed,
BINAP, a C2-symmetrical diphosphine, is outstanding due to
its broad applicability in numerous asymmetric transforma-
tions, frequently yielding products of exceptionally high enan-
tiomeric purity.1 In the past modifications of the base structure
have been undertaken in order to modify electronic and steric
properties and to adapt for new reactions and substrates. Li-
gands with partial hydrogenated biaryl systems,2 various di-
arylphosphino3 and dicyclohexylphosphino substituents,2 and
with additional substituents in remote positions of the binaph-
thyl skeleton4 have been prepared. Moreover, 2,20-unsymme-
trically substituted diphosphines5 and monophosphines6 have
been synthesized, and BINAP has been anchored to poly-
mers.7 Typically, these modifications are performed before
or together with the introduction of a PR2 group rather than
on BINAP itself, since in the latter case often side reactions
occur due to oxidation and similar reactivity of aromatic
positions. In contrast, 2,20-bis(diphenylphosphinoyl)-1,10-bi-
naphthyl [BINAP(O)2] is a stable compound and has been used
mainly as a precursor for preparing optically pure BINAP via
fractionated crystallization of diastereomeric complexes with
tartaric acid.8
While phosphines do not stabilize ortho-metallated pro-
ducts, phosphine oxides should do so but treatment with R–
Li is often accompanied by rearrangement or a rupture of
one of the P–C bonds.9 This has been used recently for the
synthesis of unsymmetrical binaphthyl monophosphine
ligands.10 Only a few examples are reported that describe
the selective ortho lithiation of phosphine oxides using phenyl
and tert-butyllithium with careful temperature control.11
Despite the increasing number of reports on ortho-metalla-
tion with LDA12;13 and other lithium or magnesium amides, no
attempt seems to have been made to use these reagents for
modifying BINAP(O)2. Here we report our findings on metal-
lation reactions of BINAP(O)2 with lithium and magnesium
dialkylamides.
Results and Discussion
The metallation of BINAP(O)2 1 is complicated by the fact
that several ortho positions are accessible in the molecule.
Treatment of 1 with various alkyllithium compounds at ꢁ78
ꢂC in THF gave immediately dark brown solutions. Under
these conditions unselective rupture of P–Car bonds takes place
rather than ortho-metallation; after quenching the reaction
with (CH3)3SiCl (TMSCl), complex mixtures of products were
obtained. In contrast, with LDA at room temperature a rear-
rangement smoothly occurred, followed by further lithiation
and formation of secondary products (Table 1). The reactions
were monitored by HPLC to elucidate their relationship and
optimize conditions for their formation. For this purpose sam-
ples of ꢃ0:1 mL were removed by syringe and quenched with
water or TMSCl. The organic phase was diluted with CH2Cl2
(1 mL), filtered through a pad of MgSO4 and analyzed. Above
ꢁ20 ꢂC the cyclized monophosphine oxide 2 was formed
quantitatively (HPLC, entry 1). Its formation can be explained
as an intramolecular SN attack of the ortho lithio intermediate
1–Li at the 2-position of naphthyl with displacement of
Ph2P(O)Li (Scheme 1). The structure was confirmed by X-
ray crystallography. With two molar amounts of LDA the re-
action was complete within 2 h. Under these conditions, none
of the products of subsequent transformations (see below) was
detected by HPLC. The solvent dependence is low and isola-
ted yields range from 66 to 70% (entry 2–5). Adding 4 mol
amt. of LDA and increasing the reaction time to 4 h gave a
lower yield of 2 (50%) and a mixture of 5 and 6 (totally
12%). Quenching the reaction at this state with TMSCl yield-
ed the silylated compound 3a at the cost of 2, while the
amount of 5 + 6 was nearly unaffected. A prolonged reaction
time led to significant decomposition of 2, possibly via 3a, and
a maximum of 16% of 5 + 6 (entry 6–9). From this we con-

1234 Bull. Chem. Soc. Jpn., 76, No. 6 (2003)
Metallation Reactions on BINAP(O)2
Table 1. Lithiation of BINAP(O)2 Products Isolated after Reaction with Water and TMSCl
Entrya)
Reagent
Mol amts.
t/h
T/ꢂC
Electrophile
7
9
2
3a
5+6
b)
8
1
2c)
3c)
4d)
5d)
6
7
8
9
LDA
LDA
LDA
LDA
LDA
LDA
LDA
LDA
2
4
2
4
2
4
4
4
4
2
8
4
2
2
2
2
2
4
3
15
3
f
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
ꢁ20
ꢁ78/r.t.
ꢁ78/r.t.
ꢁ78/r.t.
H2O
H2O
H2O
H2O
H2O
H2O
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
66
62
70
69
69
50
14
—
12
13
16
22
10
62
b)
—
Li TMP
LDA
LDA
10e)
11
12
40
0
—
—
22
73
28
b)
b)
b)
f
f
—
Li TMP
27
a) All reactions were performed on a 0.5 mmol scale in THF if not otherwise noted; for details see Experimental. In preexperiments
the progress of the reaction was monitored by HPLC. In 0.5 h intervals samples were taken and quenched with the electrophile. After
extractive work-up and drying (MgSO4) the samples were analyzed (column: Spherisorb S5W, 300 ꢄ 4:6 mm, flow: 1 mL minꢁ1 at
40 ꢂC, integration wavelength: 280 nm). Retention time (min): 1: 21.40, 2: 11.73, 3a: 3.50, 5: 8.05, 6: 8.38, 7: 10.07, 8: 3.06, 9: 2.65.
(not in the table: 4a: 6.68, 4b: 5.80, 10a: 8.36, 11a: 6.30). b) Traces c) In DMEꢂd) In dioxane e) 10–20% of unreacted starting ma-
terial recovered. f) After mixing 1, LDA, and TMSCl (excess) in THF at ꢁ78 C, the reaction was slowly warmed up to r.t. over
night.
cluded that 2 is further metallated but in a less regiospecific
manner, as the P=O group has become part of a ring.13 While
the preferential introduction of Li takes place at the naphthyl
ring, finally giving rise to 3a, also the exocyclic phenyl ring
is lithiated in position 2 (2–Li(c)). Its proximity to C-1 of
the naphthyl moiety facilitates a 1,4-addition, ending up with
a strained polycyclic structure. After hydrolysis, 6 and its iso-
mer 5 with conjugated double bonds are formed (Scheme 1).
Since both are also formed upon reaction with TMSCl we
speculate that the primary product is too unstable to be isola-
ted, decomposing under the conditions of work-up to give 5
and 6. The isomers could be separated by fractionated
crystallization. The third site for ortho lithiation, attacking
the bridging phenylene group, becomes apparent only when
quenching the reaction with less encumbered electrophiles like
DMF or CH3I. (HPLC analysis indicated a 2:1 mixture of 4a
and 4b.) Applying the more powerful and sterically demanding
nucleophile N-lithio-2,2,6,6-tetramethylpiperidine (Li-TMP) at
ꢁ20 ꢂC, a better yield of 3a was obtained. These findings re-
vealed that the ortho position of phenyl rings are preferably at-
tacked, but the high readiness for subsequent cyclization pre-
vented the synthetic use of the primarily formed lithio
compounds.
was increased to 8 mol amt., giving 73% of 8. HPLC indicated
the complete absence of 7 and that only traces of 2 and 3a were
present. With Li-TMP (4 mol amt.) further lithiation at the po-
sition 3 of naphthyl took place, giving a maximum yield of
27% of 9 along with 28% of 8. Increasing the amount of
Li-TMP did not improve the (isolable) yield of 9, since 9 be-
came a part of an inseparable mixture of polysilylated pro-
ducts.
As the application of lithio amide bases resulted in skeleton
rearrangements rather than in clean metallation reactions, we
applied the corresponding Grignard reagent, which has been
used for diastereoselective ortho magnesation.15 Stirring 1
with 4 molar amounts of 2,2,6,6-tetramethylpiperidinomagne-
sium bromide (TMP-MgBr) at room temperature for 6–12 h af-
forded a brown solution, which was quenched with Br2 or I2
(Scheme 2). Mixtures of mono- and di-halo products were
formed and could be readily separated by column
chromatography. Although the yields of 10 and 11 were mod-
erate, no skeleton transformation was observed. The diiodo
derivative 11a served as an excellent precursor for the prepara-
tion of 12 via a Suzuki reaction.
For use in asymmetric catalysis, attempts were made to con-
vert phosphineoxides 2, 3a, 8, and 12 to the corresponding
phosphines (Scheme 3). Two methods, either the addition of
methyl triflate followed by reduction with lithium aluminum
hydride,16 or reduction with aluminum hydride17 worked well
for 2, affording phosphine 13 in 98% and 85% yield,
respectively. Reoxidation of 13 to 2 with hydrogen peroxide
proceeded quantitatively. In the same way the trimethylsi-
lyl-substituted substrate 3a was smoothly reduced, giving 14
(83%). In contrast, all attempts to reduce 8 or 12 to 15 or
16, respectively failed. With TfOMe/LiAlH4, only the half-re-
duced compound 15a was isolated in low yield. This may be
attributed to steric hindrance rendering only the formation of
the mono triflate. Applying more stringent conditions or ex-
cess of alane resulted in the formation of inseparable mixtures
of low polar products.
Trapping of lithio intermediates at low temperature has been
reported by in situ reaction with electrophiles like (CH3O)3B
and TMSCl.14 Under these conditions, the electrophile is
not affected by lithio amides but reacts fast with lithiated aro-
mats, thus suppressing subsequent reactions or rearrangements.
We made use of this strategy and reacted a mixture of 1 in the
ꢂ
presence of TMSCl at ꢁ78 C with varying amounts of LDA
or Li-TMP, respectively. As above, the conversion was mon-
itored by HPLC to evaluate optimized conditions for enrich-
ment of three main products (entry 10–12). With two molar
amounts of LDA a 40% yield of 7 along with 22% of the
C2-symmetrically disubstituted product 8 could be obtained.
At this stage of the reaction, 10–20% of starting material also
remained. To make 8 the main product, the amount of LDA

M. Widhalm et al.
Bull. Chem. Soc. Jpn., 76, No. 6 (2003) 1235
Scheme 1. (Optimized yields in paranthesis).
Crystal Structure Analyses and Stereochemistry of 2, 3a,
5, 8, 9, 11a, and 13. In order to ascertain molecular structures
and to study the stereochemistry of the novel compounds, the
crystal structures of seven sufficiently well crystallizing repre-
sentatives were determined by X-ray single crystal diffraction.
Technical details on this work are reported in the experimental
section and crystallographic data are compiled in Table 2. Ac-
cording to their carbon-phosphorus backbones, the compounds
will be grouped in three classes: (A) binaphthyls with a phos-
phepine ring comprising the phosphinoyls 2 and 3a and the
phosphine 13; (B) the phosphinoyl 5 with 1,4-dihydronaphthyl
moiety and a cage-like phospha-bicyclo[3.2.2]nonane core;
and (C) the substituted 2,20-bis(diphenylphosphinoyl)-1,10-bi-
naphthyls 8, 9, and 11a. Two of these compounds crystallized
as solvates, namely 3a as a disordered DMF solvate and 11a as
a well defined and stable bis-chloroform solvate.18
The three molecules of class A compounds 2, 3a, and 13 are
shown in Figs. 1, 2, and 3, with selected geometric data pre-
sented in Table 3. One common feature of these three com-
Scheme 2. (Optimized yields in paranthesis).

1236 Bull. Chem. Soc. Jpn., 76, No. 6 (2003)
Metallation Reactions on BINAP(O)2
Fig. 2. Solid state structure of 3a in 3a DMF (20%
ꢅ
ellipsoids. H atoms omitted).
Scheme 3. (Optimized yields in paranthesis).
Fig. 3. Superposition plot of the molecular structures of 2
(full lines), 3a (dotted lines), and 13 (broken lines) in solid
state.
would result; it would become desymmetrized in the ring
and in the periphery by completing two phenyl residues to a
binaphthyl moiety. A distinct stiffness of the system becomes
apparent from the torsion angles in the 7-membered ring given
in Table 3 and from the superposition plot of 2, 3a, and 13
shown in Fig. 3. The only major freedom of the three mole-
cules is the orientation of their phenyl rings C27 through
C32 and the phosphinoyl oxygen atom or electron lone-pair
of P in 13. In all cases the respective phenyl ring is in axial
orientation relative to the boat, whereas oxygen (2, 3a) or elec-
tron lone pair (13) are equatorial. One reason for this stereo-
chemistry is that the free phenyl ring gains stabilization by
means of an intramolecular ꢀ-stacking interaction with the
naphthyl residue C11–C20, particularly so for C32–C27–C28
and less for the outer carbon atoms C29–C30–C31. In summa-
ry 2, 3a, and 13 form compact triaro[b,d,f]phosphepine mole-
cules of boat conformation and of limited flexibility. They
show an approximately mirror symmetric aspect when seen
from the phosphorus side (except for the SiMe3 group in 3a)
Fig. 1. Solid state structure of 2 (20% ellipsoids, H atoms
omitted for clarity). The solid state structure of phosphine
13, not shown, looks practically identical lacking only the
oxygen atom.
pounds is a phosphorus containing seven-membered ring built
up from three aromatic C–C, two aliphatic C–C and two P–C
bonds. The ring has a relatively regular boat conformation.
This boat conformation is a consequence of the geometric re-
strictions of three essentially planar 4-atom groups P–C2–C1–
C11, P–C21–C22–C12, and C2–C1–C12–C22 introduced by
the three aromatic ring systems that take part in the formation
of the 7-ring. If one omits the outer two phenyl rings of the
binaphthyl moiety (see Fig. 1), the saddle-like structure of a
tribenzo[b,d,f]phosphepine with potential mirror-symmetry
(m = plane defined by C27, P, and midpoint of C11–C12)

Table 2. Crystallographic Details for 2, 3a DMF, 5, 8, 9, 11a 2CHCl3, and 13
ꢅ
ꢅ
Compound
2
3a DMF
ꢅ
5
8
9
11a 2CHCl3
ꢅ
13
Formula
C32H21OP
452.46
Orthorhombic
P212121
8.458(2)
C38H36NO2PSi
597.74
Triclinic
C32H21OP
452.46
Monoclinic
P21/n
9.981(4)
11.197(4)
20.307(6)
C50H48O2P2Si2
799.00
Orthorhombic
Pbca
18.101(3)
20.908(3)
23.039(3)
C53H56O2P2Si3
871.19
Monoclinic
P21/n
30.941(17)
9.314(5)
33.934(19)
C46H32O2P2Cl6I2
1145.16
C32H21P
436.46
Triclinic
Formula weight
Crystal system
Space group
Orthorhombic
Pca21
21.079(4)
12.549(2)
17.566(3)
ꢀ
P1
ꢀ
P1
ꢁ
a/A
10.188(2)
12.195(3)
14.825(3)
104.86(2)
107.69(2)
91.95(2)
1683.5(6)
2
9.830(2)
10.939(2)
11.822(2)
111.851(3)
90.548(3)
103.535(3)
1140.6(4)
2
297
1.271
0.139
27.5
ꢁ
b/A
15.560(4)
17.427(4)
ꢁ
c/A
ꢁ/deg
ꢂ/deg
ꢃ/deg
103.06(2)
96.48(1)
ꢁ 3
V/A
2293.5(10)
4
297
1.310
0.144
27.0
2210.8(14)
4
297
1.359
0.149
25.1
8719(2)
8
183(2)
1.217
0.194
27.0
9717(9)
8
297
1.191
0.202
25.0
4646.6(14)
4
183(2)
1.637
1.805
30.0
Z
T/K
297
1.179
Dcalcd/g cmꢁ3
ꢄ(Mo Kꢁ)/mmꢁ1
0.150
25.0
ꢅmax/deg
No. of reflns collected
Transmission ratio min/max
Rint
27729
0.90
0.042
5001
4208
14623
0.92
0.018
5918
4760
343
1.080
0.041
0.124
22402
0.91
0.048
3893
2901
100459
0.91
0.039
9497
7432
48233
0.95
0.045
17013
9887
65055
0.80
0.025
13392
11740
523
1.029
0.028
0.067
ꢁ0:61/0.78
14290
0.89
0.028
5205
3866
298
1.018
0.039
0.102
No. of unique reflns
No. of observed refl [I > 2ꢆðIÞ]
No. of parameters refined
Goodness of fit
308
307
511
1082
1.024
0.035
0.082
ꢁ0:20/0.18
1.018
0.035
0.088
ꢁ0:34/0.18
1.080
0.043
0.125
ꢁ0:23/0.43
1.014
0.048
0.133
ꢁ0:24/0.23
R1 [I > 2ꢆðIÞ]
wR2 (all data)
ꢂꢇ (min/max) (eA
ꢁ ꢁ3
)
ꢁ0:29/0.18
ꢁ0:18/0.28

1238 Bull. Chem. Soc. Jpn., 76, No. 6 (2003)
Metallation Reactions on BINAP(O)2
ꢁ
Table 3. Selected Geometric Data (A and deg) for 2, 3a DMF, 13, and 5
ꢅ
2
3a DMF
13
5
ꢅ
P–O
P–C27
P–C2
P–C21
C2–C1
C1–C11
C11–C12
C12–C22
C22–C21
C11–C28
C12–C13
C13–C14
C14–C15
C3–Si
1.485(1)
1.803(2)
1.806(2)
1.805(2)
1.382(2)
1.508(2)
1.387(2)
1.491(2)
1.406(2)
1.482(1)
1.806(2)
1.809(2)
1.807(2)
1.387(2)
1.490(2)
1.389(2)
1.482(2)
1.399(2)
1.478(1)
1.769(2)
1.787(2)
1.807(2)
1.382(2)
1.554(2)
1.547(2)
1.506(3)
1.417(3)
1.564(3)
1.337(3)
1.488(3)
1.500(3)
1.836(2)
1.843(2)
1.840(2)
1.390(2)
1.500(2)
1.386(2)
1.495(2)
1.410(2)
1.426(3)
1.351(3)
1.402(3)
1.418(3)
1.354(3)
1.413(3)
1.908(2)
1.429(2)
1.359(2)
1.419(2)
C2–P–C21
C2–P–C27
C21–P–C27
100.2(1)
106.1(1)
110.0(1)
100.8(1)
110.9(1)
109.3(1)
96.2(1)
103.6(1)
106.4(1)
100.1(1)
103.1(1)
104.1(1)
C1–C2–P–C21
56.0(2)
ꢁ54.6(2)
ꢁ62.4(2)
52.5(2)
7.1(3)
13.3(2)
56.5(1)
ꢁ59.2(1)
ꢁ65.9(2)
47.5(2)
10.6(2)
14.1(2)
57.4(1)
ꢁ52.6(1)
ꢁ62.1(2)
52.0(2)
56.9(2)
ꢁ55.8(2)
ꢁ90.9(2)
24.3(2)
42.9(2)
22.2(2)
C22–C21–P–C2
C2–C1–C11–C12
C21–C22–C12–C11
C1–C11–C12–C22
C11–C1–C2–P
9.3(2)
9.4(2)
C12–C22–C21–P
C2–P–C27–C28
ꢁ12.6(2)
136.3(2)
ꢁ8.8(2)
155.1(1)
ꢁ14.0(2)
143.2(1)
ꢁ9.2(3)
22.9(2)
(Fig. 4; geometric data are included in Table 3). This addi-
tional C–C bond leads to a phospha-bicyclo[3.2.2]nonane core,
to the 1,4-dihydro-dearomatization of one phenyl ring (C11–
C15, C20) of the second naphthyl moiety, and to a pronounced
distortion of the formerly boat-shaped phosphepine ring. As a
result of the introduction of two sp3-hybridized C atoms in 1,4-
positions, the second naphthyl unit becomes bent with an angle
of 17.1(1)ꢂ between the two parts C11–C12–C13–C14 (inner
part) and C15 through C20 (outer part). Another consequence
of the steric restraints imposed by the phospha-bicyclo[3.2.2]-
nonane core is a very significant bend of the naphthyl unit C1
through C10 (to be seen from the interplanar angle between
C1–C2–C3–C4 and C5 through C10 of 13.6(1)ꢂ) and the very
large deviation of phosphorus from the mean plane of the
Fig. 4. Solid state structure of 5 in two views (20%
ellipsoids). Only the three non-aromatic H atoms are
shown.
ꢁ
naphthyl group C1 through C10, measuring 0.857 A. Thus 5
but are asymmetric on their opposite sides. Only a few other
compounds with related phosphepine rings and related stereo-
chemistry but very different synthetic backgrounds have been
reported so far. Most of them are based on the dihydro-diben-
zo[b,f]phosphepine skeleton;19 only one compound has the
tribenzo[b,d,f]phosphepine skeleton substituted by five phen-
yl rings.20 This last compound is different from 2, 3a, and 13
in being very close to mirror symmetry and in having P-phenyl
and phosphinoyl oxygen in equatorial and axial positions, re-
spectively.
is, despite its straightforward synthesis, a molecule of surpris-
ing complexity. Although there is no closely related phospho-
rus compound, it should be mentioned that some small poly-
cyclic phospha-compounds have been studied so far, such as
phosphabicyclo[3.2.1]octanes.21
The class C compounds 8, 9, and 11 are all heavily substi-
tuted BINAP(O2) derivatives, as shown in Figs. 5, 6, and 7.
They represent binaphthyls with interplanar angles not far
from 90ꢂ. Bond lengths and angles show no unusual features,
as demonstrated by a selection of geometric data presented in
Table 4. Different from class A/B compounds with low mole-
cular symmetries they come close to molecular symmetry C2.
For compounds 8 and 9, this behaviour is supported by intra-
molecular ꢀ-stacking interactions between the naphthyl moi-
The only structurally characterized compound of class B is
the phosphinoyl 5, whereas attempts to crystallize 6 for X-ray
diffraction were not successful. 5 derives from class A com-
pounds by an additional C–C bond between C11 and C28

M. Widhalm et al.
Bull. Chem. Soc. Jpn., 76, No. 6 (2003) 1239
Fig. 5. Solid state structure of 8 (40% ellipsoids, H atoms
omitted).
Fig. 7. Solid state structure of 11a 2CHCl3 (40% ellip-
ꢅ
soids) with C–H O hydrogen bonded CHCl solvent mo-
ꢅꢅꢅ
3
ꢁ
lecules, C45 O1 = 3.050(4) A, C46 O2 = 2.974(4) A.
ꢁ
ꢅꢅꢅ
ꢅꢅꢅ
Aromatic H atoms omitted.
two 2-iodophenyl moieties are mutually ꢀ-stacked and orient
the P–O bonds nearly parallel to the naphthyl-naphthyl C–C
bond. It is typical that the two phosphinoyl oxygen atoms
form clear-cut C–H Cl hydrogen bonds with two CHCl mo-
3
ꢅꢅꢅ
lecules (Fig. 7), making the solvate stable at ambient tempera-
ture.
Conclusions
Metallation of BINAP(O)2 with lithium or magnesium
amides takes place primarily at the ortho positions of one of
the phenyl rings. Subsequently, a phenyl ring of the opposite
phosphino functionality is attacked, resulting in a C2 symme-
trical species. The Grignard-type intermediates are stable at
room temperature and react with appropriate electrophiles.
The primarily formed lithium intermediates may be trapped
in situ at low temperature with TMSCl, giving rise to mono-,
di-, and trisubstituted BINAP(O)2 derivatives, while above
ꢁ40 ꢂC intramolecular ipso-substitution occurs, forming a
cyclic phosphine oxide. With excess of lithiating reagent, fur-
ther lithiation is observed, albeit with moderate site selectivity
Fig. 6. Solid state structure of 9 (20% ellipsoids, H atoms
omitted). Only the first of the two crystallographically in-
dependent but geometrically similar molecules is shown.
ety of one half molecule and a phenyl ring of the other half
molecule and vice versa, an interaction very common for
BINAP’s. In both compounds, the oxygen atoms are buried
by near SiMe3 groups and other entities, which renders their
reduction to the phosphine difficult. 11a in the form of its sol-
vate 11a 2CHCl3 shows a different conformation: here the
ꢅ
ꢁ
Table 4. Selected Geometric Data (A and deg) for 8, 9, and 11a 2CHCl3
ꢅ
ꢀ
8
9 molecule 1
9 molecule 2
11a 2CHCl3
ꢅ
P1–O1
P2–O2
C22–Si1/I1
1.487(2)
1.484(2)
1.907(2)
1.876(3)
1.914(2)
1.871(3)
1.478(2)
1.478(2)
1.925(3)
1.860(3)
1.910(3)
1.865(4)
1.925(3)
1.869(4)
1.480(2)
1.475(2)
1.920(3)
1.864(4)
1.907(3)
1.855(4)
1.919(3)
1.861(4)
1.483(2)
1.483(2)
2.103(3)
<Si1–CMe
C34–Si2/I2
>
2.108(3)
<Si2–CMe
C3–Si3
<Si3–CMe
>
>
C2–C1–C11–C12
O1–P1–C2–C1
ꢁ91:6(2)
109.7(2)
102.0(2)
ꢁ21:7(2)
ꢁ11:2(2)
ꢁ15:3(2)
ꢁ22:8(2)
ꢁ91:2(3)
134.9(2)
104.1(3)
ꢁ45:7(3)
ꢁ22:3(3)
ꢁ38:3(2)
ꢁ19:7(3)
ꢁ85:8(3)
143.8(2)
92.7(2)
ꢁ46:3(3)
ꢁ15:1(3)
ꢁ38:6(2)
ꢁ9:7(2)
95.4(3)
11.7(3)
7.2(3)
59.5(2)
61.6(2)
33.9(3)
31.4(2)
O2–P2–C12–C11
O1–P1–C21–C22
O2–P2–C33–C34
O1–P1–C27–C28
O2–P2–C39–C40
ꢀ 9 contains two independent molecules of similar conformation.

1240 Bull. Chem. Soc. Jpn., 76, No. 6 (2003)
Metallation Reactions on BINAP(O)2
(180 ꢂC): m=z 452 (Mþ, 66%). Found: C, 84.70; H, 5.07%. Calcd
for C32H21OP: C, 84.94; H, 4.68%.
and in part a second skeleton rearrangement takes place.
Structures of all key intermediates have been confirmed by
X-ray crystal structure analysis. Monophosphine oxides were
readily reduced to the corresponding phosphines, while
BINAP(O)2 derivatives afforded only partially reduced pro-
ducts in low yield.
3-Phenyl-2-trimethylsilyl-3H-benzo[b]dinaphtho[2,1-d:10,
20-f]phosphepine 3-oxide (3a). To a degassed suspension of 1
(327 mg, 0.5 mmol) in 10 mL of THF was dropwise added a so-
lution of N-lithio-2,2,6,6-tetramethylpiperidine (prepared from
372 mL of 2,2,6,6-tetramethylpiperidine and 1.25 mL of n-BuLi
in 3 mL of THF) during 15 min at ꢁ20 ꢂC; stirring was continued
Experimental
ꢂ
for 3 h. The temperature was decreased to ꢁ78 C and the reac-
Melting points: Kofler melting point apparatus, uncorrected.
NMR: Bruker AM 400 spectrometer at 400.13 MHz (1H), and
100.61 MHz (13C), respectively in CDCl3 if not otherwise noted;
chemical shifts ꢈ are reported in ppm rel. to CHCl3 (7.24 or 77.00
ppm, respectively). Coupling patterns are designated as s(inglet),
d(oublet), t(riplet), p(seudo), and b(road). 13C{1Hg NMR spectra
are recorded in a J-modulated mode; signals are assigned as C for
quaternary carbon; undesignated signals refer to CH-resonances.
In spectral areas with extensive signal overlapping, multiplets
could not be identified; these signals of unclear relationship are
underlined, ignoring probable multiplet structures. MS: MAT
900 EI (70 eV). Preparative MPLC was performed on a column
(45 ꢄ 4 cm) packed with LiChroprep-Si 60 (25–40 mm, MERCK)
using an FMI Lab Pump (1–7 bar). HPLC analyses were per-
formed on Spherisorb S5W (300 ꢄ 4:6 mm) using an HP 1090
chromatograph equipped with a diode array detector.
Petroleum ether (PE) and ethyl acetate (EA) were distilled;
absolute THF, dioxane, and DME were distilled from sodium
diphenylketyl and Et2O from LiAlH4. n-BuLi and LDA were used
as 1.6 molar (in hexane) and 1.5 molar (as THF complex in cyclo-
hexane) solutions, respectively (Aldrich). All the other chemicals
were analytical grade and were used without further purification.
BINAP(O)2 was prepared either according to Ref. 8 or by an
analogous procedure, as reported for the preparation of BINAP
from 2,20-dibromo-1,10-binaphthyl using diphenylphosphinous
chloride instead of chlorodiphenylphosphine (66%).1d
3-Phenyl-3H-benzo[b]dinaphtho[2,1-d:10,20-f]phosphepine
3-oxide (2). To a degassed solution of 1 (3.27 g, 5 mmol) in 100
mL of THF was added LDA solution (6.67 mL, 10 mmol) at 0 ꢂC
under Ar. The dark brown solution was warmed up to r.t. and stir-
red for 2 h. After 30 min a precipitate formed. The reaction was
quenched by the addition of a small amount of hydrochloric acid
(2 M) and the bulk of the solvent was evaporated. More hydro-
chloric acid (2 M, 50 mL) was added and the mixture was extrac-
ted with CH2Cl2 (3 ꢄ 50 mL). The combined extracts were wa-
shed with water (50 mL), dried with MgSO4 and evaporated.
The residue was chromatographed on SiO2 (column 30 ꢄ 5 cm)
in EA/PE (70:30) to give 1.49 g (66%) of 2; mp: 329–331 ꢂC.
1H NMR ꢈ 6.68 (m, 2H), 6.87 (m, 1H), 6.89 (bd, 1H, J ¼ 8:1
Hz), 7.06 (m, 2H), 7.17 (m, 3H), 7.36 (m, 1H), 7.44 (d, 1H, J ¼
8:6 Hz), 7.50 (m, 1H), 7.57 (m, 1H), 7.67 (m, 3H), 7.76 (m, 1H),
7.98 (d, 1H, J ¼ 8:3 Hz), 8.16 (dd, 1H, J ¼ 8:6, 1.8 Hz), 8.30
(ddd, 1H, J ¼ 12:3, 7.7, 1.4 Hz), 8.45 (dd, 1H, J ¼ 10:6, 8.3
Hz). 13C NMR ꢈ 126.03 (d, J ¼ 6:9 Hz), 126.32, 126.62,
126.82, 127.46 (d, J ¼ 13:0 Hz), 126.65, 127.68 (d, J ¼ 10:6
Hz), 128.03, 128.21, 128.24, 128.41, 128.72, 128.88 (d,
J ¼ 10:7 Hz), 129.18, 129.33 (d, J ¼ 11:5 Hz), 130.08 (d,
J ¼ 9:9 Hz), 130.72 (d, J ¼ 3:1 Hz), 131.23 (d, J ¼ 6:9 Hz),
131.65 (C, d, J ¼ 108 Hz), 132.30 (C), 132.39 (C), 132.49 (d, J ¼
2:3 Hz), 133.23 (C, d, J ¼ 3:3 Hz), 133.38 (C, d, J ¼ 11:5 Hz),
135.26 (C, d, J ¼ 2:1 Hz), 135.55 (C, d, J ¼ 138 Hz), 136.57
(C, d, J ¼ 137 Hz), 136.66 (C, d, J ¼ 10:3 Hz), 137.73 (C, d, J ¼
1:5 Hz), 142.33 (C, d, J ¼ 9:7 Hz). 31P NMR ꢈ 21.53 (s). MS
tion was quenched upon adding excess of TMSCl (4 mmol, 507
mL). After extractive work-up with hydrochloric acid (2 M, 10
mL) and CH2Cl2 (2 ꢄ 10 mL), the organic extract was dried with
MgSO4, evaporated and the residue was chromatographed on
SiO2 in EA/PE (30:70) to afford 3a as a white foam. 1H NMR
ꢈ 0.62 (s, 9H), 6.58 (m, 2H), 6.70 (d, 1H, J ¼ 8:6 Hz), 6.76 (m,
1H), 6.89 (d, 1H, J ¼ 8:6 Hz), 6.96–7.03 (m, 2H), 7.03–7.12
(m, 2H), 7.27 (m, 1H), 7.38 (d, 1H, J ¼ 8:6 Hz), 7.40 (m, 1H),
7.49 (m, 1H), 7.54–7.60 (m, 3H), 7.69 (ddd, 1H, J ¼ 7:8, 4.7,
0.8 Hz), 7.86 (d, 1H, J ¼ 8:1 Hz), 8.33 (ddd, 1H, J ¼ 12:1, 7.6,
1.0 Hz), 8.36 (d, 1H, J ¼ 1:8 Hz). 13C NMR ꢈ 2.89 (CH3),
122.44, 125.80, 126.20, 126.90, 126.90 (d, J ¼ 13:0 Hz),
127.20, 127.22, 127.29 (d, J ꢃ11 Hz), 127.58 (2 ꢄ CH),
127.98, 128.34, 128.51 (d, J ¼ 12:2 Hz), 128.72, 128.72 (d, J ¼
9:9 Hz), 129.89 (d, J ¼ 3:1 Hz), 131.70 (d, J ¼ 7:6 Hz),
ꢃ131:37 (C), 131.92 (C, d, J ¼ 105 Hz), 131.97 (d, J ¼ 2:3
Hz), 132.49 (C), 133.38 (C, d, J ¼ 12:1 Hz), 133.38 (C, d, J ¼
2:1 Hz), 136.74 (C, d, J ¼ 97:7 Hz), 137.09 (C), 137.34 (d, J ¼
14:5 Hz), 139.36 (C, d, J ¼ 105 Hz), 139.76 (C, d, J ¼ 14:5
Hz), 141.63 (C, d, J ¼ 8:3 Hz), 146.07. 31P NMR ꢈ 26.20 (s).
MS (150 ꢂC): 523 (Mþ ꢁ 1, 1%); m=z 509 (Mþ ꢁ 15, 100%).
Found: C, 79.83; H, 5.27%. Calcd for C35H29OPSi: C, 80.12; H,
5.57%.
2-Formyl-3-phenyl-3H-benzo[b]dinaphtho[2,1-d:10,20-f]-
phosphepine 3-oxide (4a) and 4-Formyl-3-phenyl-3H-ben-
zo[b]dinaphtho[2,1-d:10,20-f]phosphepine 3-oxide (4b). Lithia-
tion of 1 under the same conditions as given for the synthesis of ꢂ3a
and reaction with excess of DMF (8 mol. amt.) added at ꢁ78 C
afforded a crude mixture of 4a, 4b, and 2 which was separated by
MPLC. Elution with EA/PE (50:50) eluted 4b (9%) followed by
4a (17%). With EA/PE (70:30) 2 (27%) was eluted.
4a: Mp: 305–307 ꢂC. 1H NMR ꢈ 6.60–6.65 (m, 3H), 6.80 (m,
1H), 6.96 (d, 1H, J ¼ 8:6 Hz), 7.03–7.11 (m, 3H), 7.20 (m, 1H),
7.29 (m, 1H), 7.40 (d, 1H, J ¼ 8:6 Hz), 7.46 (m, 1H), 7.51 (m,
1H), 7.60 (m, 2H), 7.62 (d, 1H, J ¼ 8:6 Hz), 7.70 (m, 1H), 7.98
(d, 1H, J ¼ 8:3 Hz), 8.38 (ddd, 1H, J ¼ 12:4, 7.6, 1.0 Hz), 8.61
(d, 1H, J ¼ 2:8 Hz), 11.68 (s, 1H). 13C NMR ꢈ 126.08, 126.56,
127.15 (d, J ¼ 16:1 Hz), 127.20, 127.44, 127.49 (d, J ¼ 10 Hz),
127.76, 127.99, 128.21, 121.56 (d, J ¼ 12:2 Hz), 128.88, 128.98
(d, J ¼ 9:9 Hz), 129.24, 129.91 (d, J ¼ 9:5 Hz), 129.92, 130.38
(C, one branch of a doublet), 130.49 (d, J ¼ 2:3 Hz), 131.70
(C), 131.78 (C, d, J ¼ 63 Hz), 132.17 (d, J ¼ 7:6 Hz), 132.46
(C, d, J ¼ 4:0 Hz), 132.56 (d, J ¼ 2:0 Hz), 133.38 (C),
133.40 (C), 133.76 (C), 134.75 (C), 134.95 (C), 135.06 (C),
135.35 (C), 136.38 (C), 137.08 (C), 137.10 (C), 137.16 (C),
137.24 (C), 138.70 (C, d, J ¼ 11:0 Hz), 141.20 (C, d, J ¼ 9:0
Hz), 193.66 (d, J ¼ 2:3 Hz). 31P NMR ꢈ 28.18(s). MS (140
ꢂC): m=z 480 (Mþ, 8%); 452 (Mþ ꢁ 28, 100%). Found: C,
82.11; H, 4.60%. Calcd for C33H21O2P: C, 82.49; H, 4.41%.
4b: 1H NMR ꢈ 6.62 (m, 2H), 6.84 (m, 1H), 6.97 (d, 1H, J ¼
8:6 Hz), 7.02 (m, 1H), 7.06 (m, 1H), 7.14–7.23 (m, 4H), 7.35 (m,
1H), 7.48 (ddd, 1H, J ¼ 8:1, 5.8, 2.0 Hz), 7.54 (d, 1H, J ¼ 8:6
Hz), 7.60 (d, 1H, J ¼ 8:2 Hz), 7.64 (m, 1H), 7.76 (m, 1H), 7.92

M. Widhalm et al.
Bull. Chem. Soc. Jpn., 76, No. 6 (2003) 1241
(d, 1H, J ¼ 8:3 Hz), 7.98 (ddd, 1H, J ¼ 7:6, 2.8, 1.3 Hz), 8.11
(dd, 1H, J ¼ 8:6, 2.3 Hz), 8.53 (dd, 1H, J ¼ 10:9, 8.6 Hz),
11.64 (s, 1H). 13C NMR ꢈ 126.34, 126.41 (d, J ¼ 8:3 Hz),
126.66, 126.68 (d, J ¼ 2 Hz), 127.14 (d, J ¼ 13:3 Hz), 127.35
(d, J ¼ 9:2 Hz), 127.64, 127.75, 127.82, 128.06, 128.07, 128.43,
128.55 (d, J ¼ 11:0 Hz), 128.80 (d, J ¼ 11:0 Hz), 129.01,
130.65 (d, J ¼ 2:8 Hz), 130.98 (C, d, J ¼ 109 Hz), 131.42 (C,
d, J ¼ 1 Hz), 131.89 (d, J ¼ 2:3 Hz), 132.05 (C), 132.54 (C, d,
J ¼ 11 Hz), 133.05 (C, d, J ¼ 4:1 Hz), 134.09 (C, d, J ¼ 104
Hz), 134.69 (d, J ¼ 9:2 Hz), 135.05 (C, d, J ¼ 2:3 Hz), 135.72
(C, d, J ¼ 10:2 Hz), 137.10 (C, d, J ¼ 2:3 Hz), 137.33 (C, d, J ¼
95 Hz), 142.17 (C, d, J ¼ 7:0 Hz), 143.42 (C, d, J ¼ 9:7 Hz),
194.13 (d, J ¼ 2:8 Hz). 31P NMR ꢈ 28.73(s). Found: C, 81.84;
H, 4.62%. Calcd for C33H21O2P: C, 82.49; H, 4.41%.
Hz), 128.39, 129.06, 129.12 (d, J ¼ 6:1 Hz), 129.38 (C, d,
J ¼ 97 Hz), 131.07 (d, J ¼ 3:1 Hz), 131.48, 131.55 (d, J ¼ 2:3
Hz), 132.42 (C, d, J ¼ 98 Hz), 133.12 (C, d, J ¼ 14 Hz),
133.94 (C), 135.38 (C, d, J ꢃ2 Hz), 135.79 (C, d, J ¼ 10:5
Hz), 135.89, 136.54 (C), 136.61 (C, d, J ¼ 98 Hz), 140.23 (C,
d, J ¼ 10:0 Hz), 143.97 (C, d, J ¼ 8:0 Hz). 31P NMR ꢈ 17.89
ꢂ
(s). MS (160 C): m=z 452 (Mþ, 100%).
2-Diphenylphosphinoyl-20-phenyl(2-trimethylsilylphenyl)-
phosphinoyl-1,10-binaphthyl (7). To a degassed solution of 1
(327 mg, 0.5 mmol) in 30 mL of THF was added TMSCl (190
mL, 1.5 mmol) at ꢁ78 ꢂC under Ar. At the same temperature
was dropwise added LDA (0.67 mL, 1.0 mmol) during 45 min.
ꢂ
The yellow solution was stirred at ꢁ78 C for 5 h, and then al-
lowed to come to r.t. overnight. The reaction was quenched by
the addition of a small amount of hydrochloric acid (2 M) and
the solvent was evaporated. Extractive work-up with hydrochloric
acid and CH2Cl2 yielded a crude mixture of products which was
separated by MPLC in EA to afford pure 8 (86 mg, 22%) followed
by 7 (145 mg, 40%; note: due to excessive tailing the ‘‘tail’’ of the
band contained also a small impurity of 2); mp 266–268 ꢂC.
1H NMR ꢈ 0.03 (s, 9H), 6.71 (d, 1H, J ¼ 8:6 Hz), 6.81 (t, 1H, J ¼
7:6 Hz), 7.02 (bd, 1H, J ¼ 6:1 Hz), 7.04 (d, 1H, J ¼ 12:0 Hz),
7.12–7.50 (m, 19H), 7.54 (d, 1H, J ¼ 8:3 Hz), 7.59 (t, 1H,
J ¼ 7:5 Hz), 7.72 (m, 1H), 7.83–7.93 (m, 5H). 13C NMR ꢈ
1.54 (CH3), 125.67, 126.58, 126.78 (C), 127.01, 127.01 (d,
J ¼ 12:2 Hz), 127.35, 127.40, 127.47, 127.54, 127.54, 127.57,
127.64, 127.68, 127.71, 127.80, 127.91, 128.04, 129.70 (d,
J ¼ 12:2 Hz), 129.87 (C, d, J ¼ 101 Hz), 130.21 (d, J ¼ 3:1
Hz), 130.65, 130.68, 130.75, 131.68, 131.77, 131.81, 131.88,
131.90, 131.98, 132.95 (C), 133.52 (C), 133.54 (C), 133.66 (C),
133.69 (C), 133.71 (C), 133.93 (C), 133.95 (C), 134.56 (C),
135.39 (C), 135.81 (d, J ¼ 15:3 Hz), 135.74 (d, J ¼ 17:6 Hz),
136.35 (C, d, J ¼ 94 Hz), 137.36 (C, d, J ¼ 99 Hz), 143.46 (C,
m), 144.21 (C, m), 145.18 (C, d, J ¼ 15:2 Hz). 31P NMR ꢈ
28.24 (s), 34.25 (s). MS (230 ꢂC): m=z 726 (Mþ, 2.5%), 712
(Mþ ꢁ 14, 65%). Found: C, 77.23; H, 5.86%. Calcd for
C47H40O2P2Si: C, 77.66; H, 5.55%.
Cyclization Products 5 and 6. To a degassed solution of 1
(327 mg, 0.5 mmol) in 1ꢂ0 mL of THF was added LDA solution
(1.33 mL, 2 mmol) at 0 C under Ar. The dark brown solution
was warmed up to r.t. and stirred for 4 h. The reaction was
quenched by the addition of a small amount of saturated ammo-
nium chloride solution. The mixture was extracted with CH2Cl2
(3 ꢄ 10 mL) and washed with water and brine and dried with
MgSO4. After evaporation of the solvent, the residue was chro-
matographed on SiO2 (MPLC) in EA/PE (50:50) to give 28 mg
(12%) of a mixture of 5 and 6. Changing the solvent composition
to EA/PE (90:10) the subsequent eluted band contained 114 mg
(50%) of 2. Fractionated crystallization from CH2Cl2/acetone af-
forded a pure crystalline sample of 5, while 6 remained highly en-
riched in the mothꢂer liquor.
1
5: mp: ꢃ319 C (dec.) H NMR (600 MHz, CD2Cl2) ꢈ 3.98
(dd, 1H, J ¼ 23:7, 3.1 Hz), 4.08 (dd, 1H, J ¼ 23:7, 5.3 Hz),
6.37 (dd, 1H, J ¼ 7:9, 1.2 Hz), 6.53 (dd, 1H, J ¼ 8:1, 5.5 Hz),
6.71 (dd, 1H, J ¼ 5:2, 3.2 Hz), 6.91 (bpt, 1H, J ꢃ7:6 Hz), 6.99
(ddd, 1H, J ¼ 9:0, 6.8, 1.5 Hz), 7.25 (m, 1H), 7.30 (m, 1H),
7.30–7.37 (m, 3H), 7.43 (tdd, 1H, J ¼ 7:3, 2.2, 1.0 Hz), 7.44
(bd, 1H, J ꢃ9:0 Hz), 7.51 (bd, 1H, J ꢃ7:8 Hz), 7.59 (ddd, 1H,
J ¼ 8:1, 5.6, 1.0 Hz), 7.79 (bd, 1H, J ꢃ8:2 Hz), 7.90 (bd, 1H, J
ꢃ8:1 Hz), 8.02 (dd, 1H, J ¼ 13:3, 8.2 Hz), 8.04 (ddd, 1H,
J ¼ 13:7, 7.7, 1.7 Hz), 8.15 (dddd, 1H, J ¼ 12:4, 7.3, 1.5, 0.5
Hz). 13C NMR (600 MHz, CD2Cl2) ꢈ 31.51 (CH2), 55.00 (C, d,
J ¼ 9:2 Hz), 122.03 (d, J ¼ 6:1 Hz), 124.87, 126.14, 126.57,
127.02, 127.06, 127.10, 127.13 (2d), 127.28, 127.62, 127.77 (d,
J ¼ 6:1 Hz), 127.93, 128.17, 128.23 (d, J ¼ 11:2 Hz), 128.61
(d, J ¼ 10:2 Hz), 129.28, 129.33, 129.37, 129.46, 129.54 (2d),
130.10 (C, d, J ¼ 97:5 Hz), 131.51, 132.09 (C, d, J ¼ 98:5 Hz),
132.20 (d, J ¼ 2:0 Hz), 132.32 (d, J ¼ 3:1 Hz), 132.52 (C, d, J ¼
10:9 Hz), 133.22 (C), 134.93 (C, d, J ¼ 99:5 Hz), 135.20 (C),
136.69 (C, d, J ¼ 2:2 Hz), 138.85 (C, d, J ¼ 8:9 Hz), 142.21
(C, d, J ¼ 7:2 Hz), 142.53 (C), 150.75 (C, d, J ¼ 10:9 Hz).
31P NMR (CD2Cl2) ꢈ 4.97 (s). MS (210 ꢂC): m=z 452 (Mþ,
100%). Found: C, 84.65; H, 4.80%. Calcd for C32H21OP: C,
84.94; H, 4.68%.
2,20-Bis[phenyl(2-trimethylsilylphenyl)phosphinoyl]-1,10-bi-
naphthyl (8). To a degassed solution of 1 (327 mg, 0.5 mmol)ꢂin
30 mL of THF was added TMSCl (762 mL, 6 mmol) at ꢁ78 C
under Ar. This was followed by dropwise addition of LDA
(2.66 mL, 4 mmol, 8 mol. amt.) during 45 min at the same
temperature. The yellow solution was stirred at ꢁ78 ꢂC for 5
h, and then allowed to come to r.t. over night. After the same
work-up procedure as given for 7, the residue was chromato-
graphed on SiO2 (MPLC) in EA/PE (10:90) to afford a small frac-
tion (76 mg) consisting of polysilylated products and some 9 fol-
lowed by 8 (292 mg, 73%). Moreover traces of 2 and 17 mg of an
unsymmetrically disilylated product (NMR) could be isolated;
mp: 285–289 ꢂC. 1H NMR ꢈ 0.11 (s, 9H), 6.85 (m, 4H), 7.02
(m, 4H), 7.14–7.44 (m, 16H), 7.51 (dd, 2H, J ¼ 8:8, 1.5 Hz),
7.60–7.65 (m, 4H). 13C NMR ꢈ 1.70 (CH3), 126.48, 126.89,
126.94, 127.01, 127.07, 127.30, 127.59, 127.92, 127.98 (d,
J ¼ 12 Hz), 129.69 (d, J ¼ 3:1 Hz), 129.95, 129.99, 130.02,
130.05, 131.81 (bd, J ¼ 9 Hz), 131.86 (C, bd, J ¼ 100 Hz),
133.46 (C, d, J ¼ 2:4 Hz), 133.82 (d, J ¼ 15:3 Hz), 133.90 (C,
d, J ¼ 12:0 Hz), ꢃ134:8 (C, b), 136.22 (d, J ¼ 14:5 Hz),
138.43 (C, d, J ¼ 106 Hz), ꢃ141:0 (C, b), 145.77 (C, d,
J ¼ 15:0 Hz). 31P NMR ꢈ 33.35 (s). MS (240 ꢂC): m=z 798
(Mþ, 1.5%), 784 (Mþ ꢁ 14, 66%). Found: C, 75.00; H, 6.17%.
Calcd for C50H48O2P2Si2: C, 75.16; H, 6.05%.
6: 1H NMR ꢈ 5.49 (bs, 1H), 5.58 (d, 1H J ¼ 7:3 Hz), 6.57
(ptd, 1H, J ¼ 7:5, 1.3 Hz), 6.91 (d, 1H, J ¼ 9:6 Hz), 7.05 (pt,
1H, J ꢃ7:4 Hz), 7.11–7.18 (m, 2H), 7.20–7.28 (m, 2H), 7.30–
7.39 (m, 4H), 7.41 (d, 1H, J ¼ 8:8 Hz), 7.47 (bpt, 1H, J ꢃ7:7
Hz), 7.78 (d, 1H, J ¼ 8:1 Hz), 7.90 (bd, 1H, J ¼ 8:6 Hz), 7.95
(ddd, 1H, J ¼ 12:6, 7.3, 1.3 Hz), 8.01 (dd, 1H, J ¼ 7:8, 5.3
Hz), 8.13 (ddd, 1H, J ¼ 12:6, 7.3, 1.3 Hz), 8.44 (dd, 1H,
J ¼ 11:6, 8.6 Hz). 13C NMR ꢈ 52.17, 52.30 (C, d, J ¼ 7:5 Hz),
125.03, 125.20, 125.30 (d, J ¼ 6:1 Hz), 126.34, 126.74 (d,
J ¼ 9:4 Hz), 126.79, 126.93, 127.09, 127.14, 127.17, 127.26,
127.29, 127.45, 127.88 (d, J ¼ 10:7 Hz), 128.11 (d, J ¼ 10:7
2,20-Bis[phenyl(2-trimethylsilylphenyl)phosphinoyl]-3-tri-

1242 Bull. Chem. Soc. Jpn., 76, No. 6 (2003)
Metallation Reactions on BINAP(O)2
methylsilyl-1,10-binaphthyl (9). To a degassed solution of 1
(327 mg, 0.5 mmol) inꢂ 30 mL of THF was added TMSCl (762
mL, 6.0 mmol) at ꢁ78 C under Ar. At the same temperature, a
solution of N-lithio-2,2,6,6-tetramethylpiperidine (2 mmol, pre-
pared from 423 mL of 2,2,6,6-tetramethylpiperidine and 1.25
mL of n-BuLi in 10 mL of THF) was dropwise added during 45
min. The yellow solution was slowly warmed up to ꢁ25 ꢂC, stir-
red at this temperature for 5 h, and finally allowed to come to r.t.
overnight. The reaction was quenched by addition of a small
amount of hydrochloric acid (2 M). After the same work-up pro-
cedure as given for 7, the residue was chromatographed on SiO2
(MPLC) in EA/PE (10:90) to afford 9 (168 mg, 39%, 1:2 mixture
of rotamers) and 8 (113 mg, 28%). From crude 9, an analytically
pure sample was obtained by crystallization from CH2Cl2/PE.
(Partial assignment of signals to major rotamer (M) and minor ro-
tamer (m) has been performed); mp: 267–270 ꢂC. 1H NMR ꢈ
ꢁ0:16 (s, 9H, M), ꢁ0:05 (s, 9H, m), 0.21 (s, 9H, m), 0.22 (s,
9H, m), 0.32 (s, 9H, M), 0.39 (s, 9H, m), 3.70 (bs, 1H, m), 5.03
(dd, 1H, J ¼ 12:4, 7.6 Hz, M), 6.00 (m, 1H, M), 6.37 (dd, 1H,
J ¼ 14:9, 7.6 Hz, m), 6.46 (dd, 1H, J ¼ 13:9, 7.8 Hz, M), 6.49–
6.58 (m), 6.61 (d, 1H, J ¼ 8:3 Hz, m), 6.66 (pt, 1H, J ¼ 7:6
Hz, m), 6.75–7.40 (several multiplets), 7.47–7.55 (several multi-
plets),7.62–7.70 (multiple), 7.72 (dd, 1H, J ¼ 7:3, 3.0 Hz, M),
7.87 (dd, 1H, J ¼ 7:1, 2.5 Hz, m), 7.94 (d, 1H, J ¼ 2:0 Hz, M),
7.97 (d, 1H, J ¼ 8:1 Hz, m), 8.61 (bs, 1H, m), 8.92 (dd, 1H,
J ¼ 12:4, 7.8 Hz, M). 13C NMR ꢈ 1.28 (CH3, M), 1.55 (CH3,
m), 2.12 (CH3, M), 2.74 (CH3, m), 3.38 (CH3, M), 3.98 (CH3,
m), 124.06 (d, J ¼ 13:8 Hz, m), 124.25 (d, J ¼ 13:0 Hz, M),
126.1–131.0 (several multiplets), 131.38 (d, J ¼ 9:2 Hz, ?),
131.40 (C, d, J ¼ 98 Hz), 132.02 (C), 132.05 (C), 132.43 (d, J ¼
14:5 Hz, m), 132.61 (d, J ¼ 13:8 Hz, M), 132.73 (C), 132.84 (C),
133.16 (d, J ¼ 16:8 Hz, m), 133.28 (C), 133.38 (C), 133.40 (d,
J ¼ 13:8 Hz, M), 133.73 (C), 133.92 (C), 133.94 (C),
134.46 (C), 134.63 (d, J ¼ 14:5 Hz, m), 135.44 (C), 136.06 (d,
J ¼ 14:5 Hz, M), 136.94 (d, J ¼ 14:5 Hz, M), 137.37 (C),
137.66 (d, J ¼ 15:3 Hz, m), 137.80 (d, J ¼ 9:2 Hz), 138.24 (C),
138.42 (C), 138.85 (C), 138.89 (d, J ¼ 14:5 Hz, m), 138.99 (C),
139.06 (C), 139.12 (C), 139.68 (d, J ¼ 13:8 Hz, M), 140.35 (C,
d, J ¼ 105 Hz), 140.54 (C), 140.61 (C), 140.62 (C), 140.67 (C),
141.54 (C, d, J ¼ 14:2 Hz), 142.80 (C, d, J ¼ 13:2 Hz), 142.96
(C, d, J ¼ 103 Hz), 145.39 (C), 145.67 (C, d, J ¼ 16:3 Hz),
146.08 (C, d, J ¼ 16:8 Hz), 146.33 (C, d, J ¼ 15:8 Hz), 146.57
(C, d, J ¼ 15:3 Hz). 31P NMR ꢈ 29.37 (s, M), 31.92 (s, m),
34.76 (s, M), 39.38 (s, m). MS (230 ꢂC): m=z 870 (Mþ, 1%),
855 (Mþ ꢁ 15, 100%). Found: C, 73.08; H, 6.52%. Calcd for
C53H56O2P2Si3: C, 73.07; H, 6.48%.
7.71 (ddd, 2H, J ¼ 13:6, 7.8, 1.5 Hz), 7.80 (dd, 2H, J ¼ 8:6, 2.3
Hz), 7.87 (d, 2H, J ¼ 8:1 Hz). 13C NMR ꢈ 125.73 (C, d, J ¼ 106
Hz), 126.26 (d, J ¼ 11:5 Hz), 126.36, 127.18 (d, J ¼ 13:0 Hz),
127.29, 127.60, 127.80 (d, J ¼ 13:0 Hz), 128.26, ꢃ128:34 (d, J
ꢃ12 Hz), 130.78 (d, J ¼ 9:9 Hz), 131.07 (d, J ¼ 3:1 Hz),
ꢃ131:26 (C, d, J ꢃ106 Hz), 132.60 (d, J ¼ 2:2 Hz), 133.56 (d,
J ¼ 6:9 Hz), 133.79 (C, d, J ¼ 2:2 Hz), 135.20 (C, d, J ¼ 106
Hz), 135.20 (C, d, J ¼ 12 Hz), 138.64 (d, J ¼ 12:2 Hz), 145.46
(C, dd, J ꢃ5, 3.6 Hz). 31P NMR ꢈ 31.43 (s). MS (FD): m=z
812.3 (Mþ, 100%). Found: C, 65.06; H, 3.99%. Calcd for
C44H30Br2O2P2: C, 65.05; H, 3.72%.
11a:
162 mg (36%) white powder, mp ꢃ335 ꢂC (dec.).
1H NMR ꢈ 6.74 (bpt, 2H, J ¼ 7:6 Hz), 7.10 (d, 2H, J ¼ 8:6
Hz), 7.18 (bpt, 2H, J ¼ 7:6 Hz), 7.25 (bpt, 2H, J ꢃ7:8 Hz),
7.29–7.46 (m, 11H), 7.49 (bpt, 2H, J ꢃ7:5 Hz), 7.55 (dd, 2H,
J ¼ 7:8, 3.5 Hz), 7.70 (ddd, 2H, J ¼ 13:4, 7.6, 1.5 Hz), 7.78
(dd, 2H, J ¼ 8:6, 2.3 Hz), 7.85 (d, 2H, J ¼ 8:1 Hz). 13C NMR
ꢈ 99.02 (C, d, J ¼ 6:9 Hz), 125.64 (C, d, J ¼ 106 Hz), 126.40,
127.04 (d, J ¼ 12:2 Hz), 127.12 (d, J ¼ 13:0 Hz), 127.28,
127.61, 127.97 (d, J ¼ 13:0 Hz), 128.32, 128.39 (d, J ¼ 13:0
Hz), 131.10 (d, J ¼ 3:1 Hz), 131.29 (d, J ¼ 9:2 Hz), 132.33 (d,
J ¼ 2:3 Hz), 133.76 (C, d, J ¼ 106 Hz), 133.82 (C, d, J ¼ 2:0
Hz), 134.74 (C, d, J ¼ 105 Hz), 135.15 (C, d, J ¼ 12:2 Hz),
138.89 (d, J ¼ 13:0 Hz), 140.88 (d, J ¼ 9:2 Hz), 145.43 (C, dd,
ꢂ
J ¼ 6:1, 4.6 Hz). 31P NMR ꢈ 34.24(s) . MS (240 C): m=z 779
(Mþ ꢁ I, 5%).
Found: C, 57.61; H, 3.38%. Calcd for
C44H30I2O2P2: C; 58.30, H; 3.34%.
2,20-Bis[(2-biphenylyl)phenylphosphinoyl]-1,10-binaphthyl
(12). Diiodide 11a (91 mg, 0.1 mmol) was dissolved in toluene
and degassed. To this was subsequently added phenylboronic acid
(36 mg, 0.3 mmol), dissolved in a minimum quantity of EtOH
(ꢃ0:1 mL), Pd(PPh3)4 (12 mg, 0.01 mmol), and Na2CO3 solution
(2 M, 0.2 mL, ꢃ0:4 mmol). The mixture was refluxed under Ar
overnight. Work-up with H2O/CH2Cl2 yielded the crude product
which was purified by column chromatography (SiO2, 10 ꢄ 2 cm,
EA/PE/CH2Cl2, 25:25:50) to give 82 mg (ꢃ100%) of 12; mp:
319–322 ꢂC. 1H NMR ꢈ 6.81–6.94 (m, 12H), 6.97–7.06 (m,
6H), 7.12 (dd, 2H, J ¼ 11:4, 1.0 Hz), 7.15 (d, 2H, J ¼ 11:4
Hz), 7.18–7.26 (m, 4H), 7.37 (bd, 4H, J ¼ 7:1 Hz), 7.44 (m,
2H), 7.48 (dd, 2H, J ¼ 11:1, 8.6 Hz), 7.81 (dd, 2H, J ¼ 8:6, 2.3
Hz), 7.85 (d, 2H, J ¼ 8:1 Hz), 8.60 (dd, 2H, J ¼ 14:9, 7.6 Hz).
13C NMR (CDCl3) ꢈ 126.15, 126.67 (d, J ¼ 13:3 Hz), 126.87,
127.01, 127.19 (br), 127.20 (d, J ¼ 12:4 Hz), 127.45, 127.63,
127.80 (d, J ¼ 12:9 Hz), 128.04 (br), 129. 46 (C, d, J ¼ 104
Hz), 129.94 (d, J ¼ 2:8 Hz), 130.13, 130.85 (d, J ¼ 10:1 Hz),
131.18 (d, J ¼ 2:4 Hz), 131.27 (d, J ¼ 8:7 Hz), 131.40 (C, d, J ¼
102 Hz), 133.22 (C, d, J ¼ 2:2 Hz), 134.39 (C, d, J ¼ 11:7 Hz),
134.42 (C, d, J ¼ 102 Hz), 138.18 (d, J ¼ 13:3 Hz), 140.95 (C,
d, J ¼ 3:9 Hz), 144.56 (C, dd, J ¼ 5:7, 4.1 Hz), 146.22 (C, d, J ¼
8:9 Hz). 31P NMR (CDCl3) ꢈ 44.72 (s). MS (FD): m=z 806.6
(Mþ, 100%). Found: C, 82.94; H, 5.30%. Calcd for C56H40O2P2:
C, 83.36; H, 5.00%.
2,20-Bis[(2-bromophenyl)phenylphosphinoyl]-1,10-binaph-
thyl (10a) and 2,20-Bis[(2-iodophenyl)phenylphosphinoyl]-1,10-
binaphthyl (11a). General Procedure: To a degassed suspension
of 1 (327 mg, 0.5 mmol) in 6 mL of THF was added TMP-MgBr
(4 mL, 2 mmol) at r.t. under Ar. The brown solution was stirred
for 6 h, and then cooled to ꢁ78 ꢂC. The reaction was quenched by
dropwise addition of a concentrated solution of Br2 (351 mg, 112
mL, 2.2 mmol) or I2 (558 mg, 2.2 mmol) in THF (5 mL). After
warming to r.t., hydrochloric acid (2 M, 10 mL) and a small
amount of NaHSO3 was added to destroy excess reagent. Extrac-
tive work-up with CH2Cl2 (3 ꢄ 10 mL) and chromatographic
purification with SiO2 (MPLC in EA/PE, 50:50) afforded 10a
and 11a, respectively.
3-Phenyl-3H-benzo[b]dinaphtho[2,1-d:10,20-f]phosphepine
(13). To a degassed solution of 2 (100 mg, 0.22 mmol) in 4 mL
of DME was added TfOMe (82 mg, 0.5 mmol, 2.27 mol. amt., 56
mL) at r.t. under Ar. The reaction was stirred for 5 h and after 10
min precipitation of the triflate started. The mixture was cooled to
0 ꢂC, LiAlH4 (40 mg, 1.1 mmol) was added in one portion, and the
reaction was stirred overnight. Quenching with hydrochloric acid
(2 M) was followed by extractive work-up with EA. Removal of
solvent yielded almost pure 13 (96 mg, 98%) as a white powder;
10a: 159 mg (39%) white powder; mp: 252–255 ꢂC. 1H NMR
ꢈ 6.92 (bpt, 2H, J ¼ 7:6 Hz), 7.05 (bpt, 2H, J ¼ 7:6 Hz), 7.17 (d,
2H, J ¼ 7:6 Hz), 7.20–7.45 (m, 16H), 7.49 (bpt, 2H, J ꢃ7:5 Hz),
ꢂ
mp 248–251 C. 1H NMR (CD2Cl2) ꢈ 6.40–6.49 (m, 3H), 6.62–

M. Widhalm et al.
Bull. Chem. Soc. Jpn., 76, No. 6 (2003) 1243
6.68 (m, 2H), 6.92 (d, 1H, J ¼ 8:6 Hz), 7.07–7.16 (m, 3H), 7.32
(m, 1H), 7.34–7.43 (m, 2H), 7.45 (d, 1H, J ¼ 8:6 Hz), 7.54 (m,
1H), 7.60 (d, 1H, J ¼ 8:6 Hz), 7.65 (d, 1H, J ¼ 8:1 Hz), 7.76
(dd, 1H, J ¼ 7:8, 1.3 Hz), 7.91 (d, 1H, J ¼ 8:1 Hz), 7.94–8.01
(m, 2H), 8.16 (dd, 1H, J ¼ 12:9, 8.1 Hz). 13C NMR (CD2Cl2) ꢈ
125.64, 125.69, 125.95, 126.29, 126.65, 126.88 (d, J ¼ 4:6 Hz),
127.25 (d, J ¼ 17:6 Hz), 127.75, 128.03 (d, J ¼ 17:6 Hz),
128.04, 128.12 (d, J ¼ 14:5 Hz), ꢃ128:39 (d, J ꢃ3:8 Hz),
128.41 (2 ꢄ CH), 128.86, 130.79, 131.00, 132.08 (C), 132.85
(C), 132.96 (d, J ¼ 53:5 Hz), 134.28 (C, d, J ¼ 1:5 Hz), 134.49
(C), 134.53 (C), 137.06 (C, d, J ¼ 10:5 Hz), 137.16 (d,
J ¼ 53:5 Hz), 138.80 (C, d, J ꢃ4 Hz), 138.82 (C), 139.86 (C,
d, J ¼ 8:9 Hz), 141.50 (C, d, J ¼ 10:3 Hz), 144.41 (C, d, J ꢃ5
Hz). 31P NMR (CD2Cl2) ꢈ ꢁ5:42 (s). MS (100 ꢂC): m=z 436
(Mþ, 100%). Found: C, 87.30; H, 4.97%. Calcd for C32H21P:
C, 88.05; H, 4.85%.
125.87, 126.09, 127.16, 127.23, 127.29, 127.39, 127.45, 127.51,
127.55, 127.62, 127.83, 127.96, 128.10, ꢃ128.22 (C), 128.35,
128.77, ꢃ129.21 (C), 129.81 (d, J ¼ 12:2 Hz), 130.30 (d,
J ¼ 3:1 Hz), 130.80 (d, J ¼ 2 Hz), 131.25, 131.76 (d, J ¼ 9:2
Hz), 132.91 (d, J ¼ 17:6 Hz), 132.95 (C), 133.17 (C),
133.20 (C), 133.28 (C), 133.31 (C), 134.19 (d, J ¼ 16:1 Hz),
134.50 (C, d, J ¼ 2:3 Hz), 134.69, 134.73 (C), 134.80 (C),
ꢃ135:5 (C), 135.98 (d, J ¼ 14:5 Hz), ꢃ136:5 (C), 139.78 (C, d,
J ¼ 13:0 Hz), 141.97 (C, d, J ¼ 14:0 Hz), 144.79 (C),
144.85 (C), 146.33 (C, d, J ¼ 15:5 Hz), 146.92 (C, d, J ¼ 47:8
Hz). 31P NMR (CDCl3) ꢈ 33.43 (brs); ꢁ17:42 (s). MS (FAB):
m=z 783.4 (Mþ + 1, 100%). Found: C, 76.42; H, 6.43%. Calcd
for C50H48OP2Si2: C, 76.69; H, 6.18%.
X-ray Structure Determinations of 2, 3a DMF, 5, 8, 9,
11a 2CHCl , and 13. X-ray diffraction measurements were
ꢀ
made on a Bruker AXS SMART platform 3-circle diffractometer
ꢀ
equipped with a CCD area detector, using graphite-monochroma-
3
2-Trimethylsilyl-3-phenyl-3H-benzo[b]dinaphtho[2,1-d:10,
20-f]phosphepine (14). To a degassed solution of 3a (115 mg,
0.22 mmol) in 1 mL of DME was added TfOMe (41 mg, 0.25
mmol, 1.13 mol. amt., 28 mL) at r.t. under Ar. The reaction
was stirred for 5 h and then cooled to 0 ꢂC. LiAlH4 (20 mg,
0.55 mmol) was added in one portion and the reaction was stirred
overnight. Quenching with hydrochloric acid (2 M) was followed
by extractive work-up with EA. After drying (MgSO4) and eva-
poration of solvent, the crude product was purified by MPLC on
SiO2 in EA/PE (10:90) to yield 96 mg (83%) of 14. From a sec-
ond band, 11 mg (10%) of unreacted 3a have been recovered; mp
ꢃ278 ꢂC. 1H NMR ꢈ 0.64 (d, 9H, J ¼ 2:0 Hz), 6.34–6.44 (m,
3H), 6.61 (m, 2H), 6.80 (d, 1H, J ¼ 8:6 Hz), 6.95 (d, 1H,
J ¼ 8:6 Hz), 7.00–7.09 (m, 2H), 7.24 (m, 1H), 7.28–7.36 (m,
2H), 7.40 (d, 1H, J ¼ 8:6 Hz), 7.47 (m, 1H), 7.52 (d, 1H,
J ¼ 8:6 Hz), 7.56 (d, 1H, J ¼ 7:6 Hz), 7.73 (d, 1H, J ¼ 7:6
Hz), 7.82 (d, 1H, J ¼ 8:6 Hz), 7.93 (ddd, 1H, J ¼ 14:1, 7.6, 1.3
Hz), 8.12 (d, 1H, J ¼ 2:5 Hz). 13C NMR ꢈ 1.80 (CH3, d,
J ¼ 11:0 Hz), 125.01, 125.17, 125.49, 126.20, 126.34, 126.44
(d, J ¼ 3:8 Hz), 126.73 (d, J ¼ 17:6 Hz), 127.31, 127.55,
127.61 (d, J ¼ 16:8 Hz), 128.01, 128.03, 128.13, 128.23,
130.04, 130.53, 131.54 (C), 132.77 (C), 132.93 (C, d, J ¼ 1:5
Hz), 134.49 (C), 134.76 (C), 135.03 (d, J ¼ 19:1 Hz), 136.71
(C, d, J ¼ 12:0 Hz), 136.94 (d, J ¼ 53:5 Hz), 138.31 (C),
139.12 (C, d, J ¼ 3:1 Hz), 140.74 (C, d, J ¼ 11:2 Hz), 143.59
(C, d, J ¼ 52:5 Hz), 144.42 (C), 144.44 (C, d, J ¼ 12:3 Hz).
31P NMR ꢈ ꢁ15:37 (s). MS (150 ꢂC): m=z 508 (Mþ, 100%).
Found: C, 82.40; H, 5.97%. Calcd for C35H29PSi: C, 82.64; H,
5.75%.
ꢁ
ted Mo Kꢁ radiation (ꢉ ¼ 0:71073 A). Complete spheres of dif-
fraction data were collected using !-scans of 0.3ꢂ (0.2ꢂ and a
hemisphere for 9). Cell dimensions were obtained by least-
squares refinements using the measured positions of about 1000
strong reflections. The frame data were integrated and corrected
for Lorentz and polarization effects using the program SAINT.22
Empirical absorption corrections based on measurements of multi-
ply redundant data were performed using program SADABS.22
The structures were solved with direct methods, expanded with
Fourier techniques, and refined by full matrix least squares on
F2 with all reflections using the SHELXTL programs.22 Non-hy-
drogen atoms were refined anisotropically and hydrogen atoms
were included in calculated positions and refined with the riding
model. A secondary extinction correction was applied if ap-
propriate. For 3a DMF, the solvent was found to be disordered
ꢅ
and was modeled with the SQUEEZE procedure of program
PLATON.23 Crystallographic data are summarized in Table 2.
References
1
a) D. Cai, J. F. Payack, D. R. Bender, D. L. Hughes, T. R.
Verhoeven, and P. J. Reider, J. Org. Chem., 59, 7180 (1994). b) H.
Kumobayashi, Recl. Trav. Chim. Pays-Pas, 115, 201 (1996). c) R.
Noyori and H. Takaya, Acc. Chem. Res., 23, 345 (1990). d) A.
Miyashita, H. Takaya, T. Souchi, and R. Noyori, Tetrahedron,
40, 1245 (1984). e) A. Miyashita, A. Yasuda, H. Takaya, K.
Toriumi, T. Ito, T. Souchi, and R. Noyori, J. Am. Chem. Soc.,
102, 7932 (1980).
2-[Phenyl(2-trimethylsilylphenyl)phosphino]-20-[phenyl(2-
trimethylsilylphenyl)phosphinoyl]-1,10-binaphthyl (15a). To a
degassed solution of 8 (200 mg, 0.25 mmol) in 7 mL of DME was
added TfOMe (98 mg, 0.6 mmol, 1.2 mol. amt., 68 mL) at r.t. un-
der Ar. The reaction was stirred for 6 h; after 10 min, precipita-
tion of the triflate started. The mixture was cooled to ꢁ35 ꢂC and
LiAlH4 (52 mg, 1.3 mmol) was added. After the precipitate has
dissolved during 1 h, the dark red reaction was kept between
ꢁ10 ꢂC and ꢁ20 ꢂC overnight. The reaction was quenched by
the addition of a small amount of hydrochloric acid (2 M). Ex-
tractive work-up with EA and chromatographic separation of the
residue on SiO2 (MPLC, EA/PE, 10:90) afforded 25–30% (49–
59 mg) of 15a; mp: 288–291 ꢂC. 1H NMR ꢈ ꢁ0:39 (d, 9H,
J ¼ 1:3 Hz), 0.07 (s, 9H), 6.30–6.45 (m, 4H), 6.95–7.40 (m,
19H), 7.52 (dd, 1H, J ¼ 13:9, 7.6 Hz), 7.56 (dd, 1H, J ¼ 11:4,
8.6 Hz), 7.65–7.75 (m, 4H), 7.83 (dd, 1H, J ¼ 8:6, 1.8 Hz).
13C NMR ꢈ 0.44 (CH3, d, J ¼ 8:4 Hz), 1.74 (CH3), 125.14,
2
a) X. Zhang, K. Mashima, K. Koyano, N. Sayo, H.
Kumobayashi, S. Akutagawa, and H. Takaya, J. Chem. Soc., Per-
kin Trans. 1, 1994, 2309. b) X. Zhang, K. Mashima, K.
Koyano, N. Sayo, H. Kumobayashi, S. Akutagawa, and H.
Takaya, Tetrahedron Lett., 32, 7283 (1991). c) H. Takaya, K.
Mashima, K. Koyano, M. Yagi, H. Kumobayashi, T. Taketomi,
S. Akutagawa, and R. Noyori, J. Org. Chem., 51, 629 (1986).
3
a) N. G. Andersen, R. Mc Donald, and B. A. Keay, Tetra-
hedron: Asymmetry, 12, 263 (2001). b) T. Senda, M. Ogasawara,
and T. Hayashi, J. Org. Chem., 66, 6852 (2001). c) K. Mashima,
K. Kusano, N. Sato, Y. Matsumura, K. Nozaki, H. Kumobayashi,
N. Sayo, Y. Hori, T. Ishizaki, S. Akutagawa, and H. Takaya, J.
Org. Chem., 59, 3064 (1994). d) see Ref. 2c.
4
a) P. Guerreiro, V. Ratovelomanana-Vidal, J.-P. Genet, and
P. Dellis, Tetrahedron Lett., 42, 3423 (2001). b) D. J. Birdsall, E.
G. Hope, A. M. Stuart, W. Chen, Y. Hu, and J. Xiao, Tetrahedron
Lett., 42, 8551 (2001). c) R. Halle, B. Colasson, E. Schulz, M.

1244 Bull. Chem. Soc. Jpn., 76, No. 6 (2003)
Metallation Reactions on BINAP(O)2
Spagnol, and M. Lemaire, Tetrahedron Lett., 41, 643 (2000). d) D.
Che, N. G. Andersen, S. Y. W. Lau, M. Parvez, and B. A. Keay,
Tetrahedron: Asymmetry, 11, 1919 (2000).
20 (1989).
a) O. Desponds and M. Schlosser, J. Organomet. Chem.,
9
507, 257 (1996). b) S. Ogawa, Y. Tajiri, and N. Furukawa, Bull.
Chem. Soc. Jpn., 64, 3182 (1991). c) B. Schaub, T. Jenny, and
M. Schlosser, Tetrahedron Lett., 25, 4097 (1984). d) D. Seyferth,
D. E. Welch, and J. K. Heeren, J. Am. Chem. Soc., 86, 1100
(1964).
5
a) S. Gladiali, A. Dore, D. Fabbri, S. Medici, G. Pirri, and
S. Pulacchini, Eur. J. Org. Chem., 2000, 2861. b) T. Hayashi, T.
Senda, Y. Takaya, and M. Ogasawara, J. Am. Chem. Soc., 121,
11591 (1999).
6
a) T. Hamada and S. L. Buchwald, Org. Lett., 4, 999
10 T. Shimada, H. Kurushima, Y.-H. Cho, and T. Hayashi, J.
Org. Chem., 66, 8854 (2001).
(2002). b) Y. Wang, X. Li, and K. Ding, Tetrahedron Lett., 43,
159 (2002). c) T. Hayashi, J. W. Han, A. Takeda, J. Tang, K.
Nohmi, K. Mukaide, H. Tsuji, and Y. Uozumi, Adv. Synth. Catal.,
343, 279 (2001). d) M. Cavazzini, G. Pozzi, S. Quici, D. Maillard,
and D. Sinou, Chem. Commun., 2001, 1220. e) D. Bonafoux, Z.
Hua, B. Wang, and I. Ojima, J. Fluorine Chem., 112, 101
(2001). f) G. Francio, K. Wittmann, and W. Leitner, J. Organo-
met. Chem., 621, 130 (2001). g) Y. Wang, H. Guo, and K. Ding,
Tetrahedron: Asymmetry, 11, 4153 (2000). h) M. Kawatsura, Y.
Uozumi, M. Ogasawara, and T. Hayashi, Tetrahedron, 56, 2247
(2000). i) H. Kodama, T. Taiji, T. Ohta, and I. Furukawa, Tetra-
hedron: Asymmetry, 11, 4009 (2000). j) K. Sumi, T. Ikariya, and
R. Noyori, Can. J. Chem., 78, 697 (2000). k) T. Hayashi and M.
Ishigedani, J. Am. Chem. Soc., 122, 976 (2000). l) X. Hu, H. Chen,
and X. Zhang, Angew. Chem., 38, 3518 (1999). m) K. Ding, Y.
Wang, H. Yun, J. Liu, Y. Wu, M. Terada, Y. Okubo, and K.
Mikami, Chem. Eur. J., 5, 1734 (1999). n) K. Nozaki, F.
Shibahara, Y. Itoi, E. Shirakawa, T. Ohta, H. Takaya, and T.
Hiyama, Bull. Chem. Soc. Jpn., 72, 1911 (1999). o) S. Gladiali,
S. Pulacchini, D. Fabbri, M. Manassero, and M. Sansoni, Tetrahe-
dron: Asymmetry, 9, 391 (1998). p) S. Vyskocil, M. Smrcina, V.
Hanus, M. Polasek, and P. Kocovsky, J. Org. Chem., 63, 7738
(1998). q) S. Y. Cho and M. Shibasaki, Tetrahedron Lett., 39,
1773 (1998). r) A. Ashimori, B. Bachand, M. A. Calter, S. P.
Govek, L. E. Overman, and D. J. Poon, J. Am. Chem. Soc., 120,
6488 (1998). s) M. Ogasawara, K. Yoshida, H. Kamei, K. Kato,
Y. Uozumi, and T. Hayashi, Tetrahedron: Asymmetry, 9, 1779
(1998). t) Y. Imai, W. Zhang, T. Kida, Y. Nakatsuji, and I. Ikeda,
Tetrahedron Lett., 39, 4343 (1998). u) K. Nozaki, N. Sakai, T.
Nanno, T. Higashijima, S. Mano, T. Horiuchi, and H. Takaya, J.
Am. Chem. Soc., 119, 4413 (1997). v) R. Kadyrov, J. Heinicke,
M. K. Kindermann, D. Heller, C. Fischer, R. Selke, A. K. Fischer,
and P. G. Jones, Chem. Ber., Recl., 130, 1663 (1997). w) T.
Horiuchi, T. Ohta, E. Shirakawa, K. Nozaki, and H. Takaya, J.
Org. Chem., 62, 4285 (1997). x) K. Inagaki, T. Ohta, K. Nozaki,
and H. Takaya, J. Organomet. Chem., 531, 159 (1997). y) T.
Hattori, M. Shijo, J. Sakamoto, S. Kumagai, A. Nakajima, and
S. Miyano, J. Chem. Res. Miniprint, 1995, 124. z) S. Gladiali,
A. Dore, and D. Fabbri, Tetrahedron: Asymmetry, 5, 1143
(1994). aa) T. Hattori, J. Sakamoto, N. Hayashizaka, and S.
Miyano, Synthesis, 1994, 199. bb) Y. Uozumi, N. Suzuki, A.
Ogiwara, and T. Hayashi, Tetrahedron, 50, 4293 (1994). cc) N.
Sakai, S. Mano, K. Nozaki, and H. Takaya, J. Am. Chem. Soc.,
115, 7033 (1993). dd) Y. Uozumi, A. Tanahashi, S.-Y. Lee, and
T. Hayashi, J. Org. Chem., 58, 1945 (1993). ee) Y. Uozumi and
T. Hayashi, J. Am. Chem. Soc., 113, 9887 (1991). ff) K. J. Brown,
M. S. Berry, K. C. Waterman, D. Lingenfelter, and J. R. Murdoch,
J. Am. Chem. Soc., 106, 4717 (1984).
11 a) see Ref. 9a. b) J. M. Brown and S. Woodward, J. Org.
Chem., 56, 6803 (1991). c) M. Gray, B. J. Chapell, N. J. Taylor,
and V. Snieckus, Synlett, 1988, 422.
12 a) S. E. Gibson, H. Ibrahim, C. Pasquier, and J. W. Steed,
Tetrahedron, 58, 4617 (2002). b) R. J. Mattson, C. P. Sloan, C. C.
Lockhart, J. D. Catt, Q. Gao, and S. Huang, J. Org. Chem., 64,
8004 (1999). c) I. R. Butler, S. Mussig, and M. Plath, Inorg.
¨
Chem. Commun., 2, 424 (1999). d) F. Mongin, O. Desponds,
and M. Schlosser, Tetrahedron Lett., 37, 2767 (1996). e) O.
Desponds, Chimia, 50, 639 (1996). f) F. Mongin and M.
Schlosser, Tetrahedron Lett., 37, 6551 (1996). g) Y.-G. Gu and
E. K. Bayburt, Tetrahedron Lett., 37, 2565 (1996). h) C.
´
Cochennec, P. Rocca, F. Marsais, A. Godard, and G. Queguiner,
Synthesis, 1995, 321. i) Y. Aoyagi, T. Inariyama, Y. Arai, S.
Tsuchida, Y. Matuda, H. Kobayashi, A. Ohta, T. Kurihara, and
S. Fijihara, Tetrahedron, 50, 13575 (1994). j) P. Rocca, C.
Cochennec, F. Marsais, L. Thomas-dit-Dumont, M. Mallet, A.
´
Godard, and G. Queguiner, J. Org. Chem., 58, 7832 (1993). k)
R. R. Goehring, Tetrahedron Lett., 33, 6045 (1992). l) F. Marsais,
P. Pineau, F. Nivolliers, M. Mallet, A. Turck, A. Godard, and G.
´
Queguiner, J. Org. Chem., 57, 565 (1992).
13 S. Ogawa, Y. Tajiri, and N. Furukawa, Bull. Chem. Soc.
Jpn., 64, 3182 (1991).
14 T. D. Krizan and J. C. Martin, J. Am. Chem. Soc., 105,
6155 (1983).
15 a) U. Nettekoven, M. Widhalm, P. C. J. Kamer, P. W. N.
M. van Leeuwen, K. Mereiter. M. Lutz, and A. L. Spek, Organo-
metallics, 19, 2299 (2000). b) M. Sawamura, A. Yamauchi, and Y.
Ito, J. Chem. Soc., Chem. Commun., 1991, 874. c) P. E.
Eaton, C. Lee, and Y. Xiong, J. Am. Chem. Soc., 111, 8016
(1989).
16 T. Imamoto, S. Kikuchi, T. Miura, and Y. Wada, Org.
Lett., 3, 87 (2001).
17 a) A. Bootle-Wilbraham, S. Head, J. Longstaff, and P.
Wyatt, Tetrahedron Lett., 40, 5267 (1999). b) S. Griffin, L. Heath,
and P. Wyatt, Tetrahedron Lett., 39, 4405 (1998).
18 Compound 3a is prone to form various solvates (e.g. with
CH2Cl2, DMF). In addition to 3a DMF a second crystalline form
ꢅ
3a 1/2DMF was obtained, studied with X-ray diffraction, and
structural data were deposited under CCDC-194684.
ꢅ
19 a) P. Wyatt, S. Warren, M. McPartlin, and T. Woodroffe, J.
Chem. Soc., Perkin Trans. 1, 2001, 279. b) D. W. Allen, I. W.
Nowell, and P. E. Walker, Z. Naturforsch.,Teil B, 35, 133 (1980).
20 W. Winter, Chem. Ber., 111, 2942 (1978); For related or-
ganometallics see also: E. Luppold and W. Winter, Chem. Ber.,
116, 1923 (1983).
21 B. Krauss, C. Mugge, B. Ziemer, A. Zschunke, and F.
Krech, Z. Anorg. Allg. Chem., 627, 1542 (2001).
7
a) Q.-H. Fan, R. Wang, and A. S. C. Chan, Bioorg. & Med.
Chem. Lett., 12, 1867 (2002). b) C. Saluzzo, T. Lamouille, F. Le
Guyader, and M. Lemaire, Tetrahedron: Asymmetry, 13, 1141
(2002). c) D. J. Baystone, J. L. Fraser, M. R. Ashton, A. D. Baxer,
M. E. C. Polywka, and E. Moses, J. Org. Chem., 63, 3137 (1998).
22 Bruker, Programs SMART, version 5.054; SAINT, version
6.2.9; SADABS version 2.03; XPREP, version 5.1; SHELXTL,
version 5.1./Bruker AXS Inc., Madison, WI, USA, 2001.
23 A. L. Spek (1990): PLATON-A Multipurpose Crystallo-
graphic Tool. Utrecht University, Utrecht, The Netherlands.
8
H. Takaya, S. Akutagawa, and R. Noyori, Org. Synth., 67,