Synthesis and characterization of 4- and 4,4′-phosphorylated 2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyls

Article abstract of DOI:10.1002/1099-0690(200102)2001:3<477::AID-EJOC477>3.0.CO;2-3

A convenient reaction sequence has been established to obtain selectively the mono- or bisphosphorylated BINAP derivatives 6-9. The structure of the new compounds was confirmed by NMR spectroscopy. The sodium salts of the phosphonic acid derivatives 8 and

Full text of DOI:10.1002/1099-0690(200102)2001:3<477::AID-EJOC477>3.0.CO;2-3

SHORT COMMUNICATION
Synthesis and Characterization of 4- and 4,4Ј-Phosphorylated
2,2Ј-Bis(diphenylphosphanyl)-1,1Ј-binaphthyls
Michael Kant,*[a] Stefan Bischoff,[a] Rolf Siefken,[a] Egon Gründemann,[a] and
Angela Köckritz*[a]
Keywords: BINAP / Phosphorylations / Phosphanes / Asymmetric catalysis / Biphasic catalysis / NMR spectroscopy
A convenient reaction sequence has been established to ob-
firmed by NMR spectroscopy. The sodium salts of the phos-
tain selectively the mono- or bisphosphorylated BINAP de- phonic acid derivatives 8 and 9 can be used in aqueous bi-
rivatives 6−9. The structure of the new compounds was con-
phasic catalysis.
Introduction
Catalytic hydroformylations of olefins in the homogen-
eous phase as well as in aqueous biphasic systems have be-
come large-volume technical processes to produce
aldehydes.[1Ϫ3] However, asymmetric hydroformylation, re-
sulting in valuable chiral aldehydes as intermediates for fine
chemicals, still requires further efforts for catalyst develop-
ment. Numerous homogeneous catalysts have been investig-
ated in this reaction but the majority of them showed only
low or moderate selectivities. The best chiral homogeneous
hydroformylation catalysts are formed with ligands con-
taining phosphite groups, such as Takaya’s BINAPHOS
[(R)-2-(diphenylphosphanyl)-1,1Ј-binaphthalen-2Ј-yl-(S)-
1,1Ј-binaphthalene-2,2Ј-diyl phosphite],[4Ϫ7] bulky diphos-
phite ligands[8,9] or a phosphane-phosphite developed by
van Leeuwen.[10] Despite their exceptional catalytic proper-
ties these ligands suffer from instability against traces of
water. Furthermore, their preparation and purification is
complex and expensive. Thus, bisphosphanes which are
stable against hydrolysis have attracted renewed attention.
In contrast to previous results[11,12] recently published in-
vestigations[13] showed that rhodium bisphosphane catalysts
can reach enantiomeric excesses (ee) of up to 76% in the
asymmetric hydroformylation of styrene. Therefore, further
attempts should be directed to the development of new, effi-
cient chiral bisphosphanes.
During our investigations on hydroformylation in aque-
ous biphasic systems and over heterogenized complexes we
succeeded in the functionalization of a series of tertiary
aryl- and arylalkylphosphanes with phosphonate
groups.[14Ϫ16]
Phosphorylated
alkyldiarylphosphanes
showed an outstanding performance in the hydroformyl-
ation of higher terminal olefins[14] in aqueous biphasic sys-
tems, which offer several technological advantages,[2,3] espe-
cially simplified catalyst recycling. To expand the applica-
tion field of phosphorylated ligands to asymmetric hydro- Scheme 1. Synthesis of phosphorylated 2,2Ј-bis(diphenylphos-
phanyl)-1,1Ј-binaphthyls
formylation in biphasic systems, we developed new methods
[a]
Institute for Applied Chemistry Berlin-Adlershof,
to introduce phosphonate groups to a well-known atropi-
someric ligand — BINAP [2,2Ј-bis(diphenylphosphanyl)-
1,1Ј-binaphthyl] — as described below.
Richard-Willstätter-Str. 12, 12489 Berlin, Germany
E-mail: koeck@aca-berlin.de
kant@aca-berlin.de
Eur. J. Org. Chem. 2001, 477Ϫ481
WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
1434Ϫ193X/01/0203Ϫ0477 $ 17.50ϩ.50/0
477

M. Kant, S. Bischoff, R. Siefken, E. Gründemann, A. Köckritz
SHORT COMMUNICATION
BINAP is accessible in its chiral R and S forms.[17] It is caused low conversion, while long times led to an undesired
one of the best examined and most successful chiral chelat- reduction of the phosphonate group. The bisphosphanes 6
ing ligands and has gained industrial importance for homo- and 7 were purified by column chromatography (6) or
geneous catalysis.[18,19] However, sulfonation of BINAP or recrystallized (7). Final hydrolysis of the dialkyl phosphon-
similar atropisomeric bisphosphanes to obtain water-sol- ate groups resulted quantitatively in the phosphonic acid-
uble ligands does not lead to the pure products, but to mix- substituted BINAP derivatives 8 and 9. The 31P NMR spec-
tures of different isomers.[20,27] Other methods to make BI- trum of 8 in S-(Ϫ)-1-phenylethylamine showed the signals
NAP water-soluble have been reported,[21,22] but to the best of only one pure diastereomeric salt at δ ϭ Ϫ15.0 (J ϭ
of our knowledge enantiopure water-soluble BINAP deriv- 4.7 Hz) and δ ϭ Ϫ16.4 (J ϭ 6.1 Hz) (phosphane groups) as
atives have not been used for catalytic hydroformylation as well as at δ ϭ 6.4 (phosphonium salt). Thus, racemization
yet.
during the described reaction sequence can be ruled out.
Structure Determination of the New Ligands
Results and Discussion
The position of the phosphonic ester group in the bi-
Starting from (R)-BINAP oxide[17] (1) we developed a naphthyl skeleton was determined by NMR spectroscopy.
four-stage method for the functionalization of BINAP with A comparison of the 1H NMR spectra of the unsubstituted
phosphonic acid groups (Scheme 1).
BINAP oxide 1 and the bisphosphorylated phosphane ox-
1
Bromination of 1 in the presence of pyridine resulted in ide 5, as well as the interpretation of the H-COSY spec-
the monobrominated product 2 after the first run. The two- trum of 5 (Figure 1), allowed the structure determination
fold repetition of the brominating procedure with crude 1 of this compound. The monobrominated product 2 is an
and fresh bromine gave the bisbrominated compound 3. intermediate product in the bromination of 1 to 3. There-
Pyridine was added to eliminate hydrobromic acid from the fore the position of the phosphonic ester group in 4 must
reaction mixture thus avoiding conditions which could be the same as in 5.
cause racemization.[23] The introduction of phosphonate
The 1H NMR spectrum of 1 shows an ABCD pattern for
groups succeeded with modified palladium-catalysed reac- the HA, HB, HC and HD protons in the annelated ring, as
tions of 2 and 3 with diethylphosphite.[24] The reduction of does the spectrum of 5. Additionally, the ABCD coupling
the phosphorylated phosphane oxides 4 and 5 to the corres- pattern was supported by simulation. As can be seen from
ponding phosphanes was carried out with phenylsilane as Figure 1, four binaphthylic hydrogen nuclei (HA, HB, HC
reducing agent.[25] For this step it was necessary to optimize and HD) of 5 exist, each one of them coupling with at least
the reaction time because too short a time for reduction one neighbouring hydrogen nucleus. This implies that the
1
Figure 1. H COSY spectrum of 5
478
Eur. J. Org. Chem. 2001, 477Ϫ481

4- and 4,4Ј-Phosphorylated 2,2Ј-Bis(diphenylphosphanyl)-1,1Ј-binaphthyls
SHORT COMMUNICATION
Na2SO4 was followed by filtration. After evaporation of the solv-
ent, the crude oily product which mainly consisted of the 4-bromo-
substituted product 2 was used for its phosphorylation to 4.
phosphorylation occurred either in the 3- or the 4-position.
One proton (HE) does not couple with any other hydrogen.
1H-31P coupling experiments showed that this ‘‘special’’ hy-
drogen nucleus couples with both phosphorus nuclei to a
similar extent (J ϭ 16.6 and 11.7 Hz),[26] which means that
HE must be located in the direct vicinity of both phos-
phorus substituents. This is only the case for a proton in
the 3-position. Furthermore, 3JPCCH and 4JPCCCH for a pro-
ton in the 4-position should be very different in size, which
is not the case.
Yield: 16.83 g (consisting of 62 mol-% of 2, 18 mol-% of 3 and 20
mol-% of 1, determined by 31P NMR spectroscopy). Ϫ 31P NMR
(CH2Cl2): δ ϭ 26.8, 28.0.
To obtain the bisbrominated product 3, the above described brom-
ination procedure was repeated twice and the crude products of the
preceding brominations, containing 2, were used as starting mat-
erials. The dichloromethane solution of 3 was reduced in volume,
and the crude oily product was dried in vacuo and used for the
following phosphorylation to obtain 5.
From these findings we deduced the structure for the
phosphorylated BINAP oxides described in Scheme 1. This
is in agreement with the rules for electrophilic aromatic sub-
Yield: 18.43 g (consisting of 86 mol-% of 3 and 14 mol-% of 2,
stitutions. Surprisingly, substitution did not take place determined by 31P NMR spectrosocpy). Ϫ 31P NMR (CH2Cl2):
δ ϭ 26.5.
either in the positions 6 or 7 of the binaphthyl nor in the
phenyl rings.
(R)-(؉)-4-Diethoxyphosphoryl-2,2Ј-bis(diphenylphosphoryl)-1,1Ј-
binaphthyl (4): Crude 2 (7.34 g containing 6.2 mmol of 2), diethyl
phosphite (4.88 g, 40 mmol), tetrakis(triphenylphosphane)pallad-
ium (1.15 g, 1 mmol) and triethylamine (4.04 g, 40 mmol) were dis-
solved in absolute toluene (20 mL) and stirred for 22 hours at 90
°C. After cooling, the solution was diluted with CH2Cl2 (80 mL),
extracted three times with H2O (30 mL) and dried with Na2SO4.
The solvent was evaporated and the crude product chromato-
graphed on a silica gel column (eluent: ethyl acetate/hexane/eth-
anol, 7:3:1) giving a colourless oil. Yield: 2.65 g (54%). Ϫ MS:
Conclusion
We have developed a convenient method to obtain select-
ively phosphorylated binaphthyl derivatives. Depending on
the reaction conditions, one or two phosphonate groups can
be introduced into binaphthyl structures. The solubility of
the phosphonic acids 8 and 9 in water is moderate but the
solubility of their sodium salts is excellent. So the new
chiral BINAP ligands can be used both in biphasic catalysis
and in heterogeneous catalysis with complexes anchored via
the phosphonic acid groups. The catalytic properties of the
new ligands will be published elsewhere next.
1
(m/z) ϭ 791 [Mϩ ϩ 1]. Ϫ [α]2D0 ϭ ϩ98.6 (DMSO, c ϭ 1.0). Ϫ H
NMR (CDCl3): δ ϭ 1.24, 1.26 (2t, 6 H, CH3), 4.07 (m, 4 H, CH2),
6.64 (d, J ϭ 8.5, 1 H), 6.74 (m, 3 H), 7.21 (m, 4 H), 7.30Ϫ7.45 (m,
15 H), 7.65Ϫ7.78 (m, 4 H) 7.82 (d, J ϭ 7.9, 1 H), 7.88 (dd, J ϭ
8.5, 2.4, 1 H), 8.04 (dd, J ϭ 16.5, 11.6, 1 H), 8.59 (d, J ϭ 8.8, 1
H, CHnaphthyl ϩ CHphenyl). Ϫ 13C NMR (CDCl3): δ ϭ 16.2, 16.3
(CH3), 62.4 (d, J ϭ 5.5), 62.6 (d, J ϭ 5.9, CH2), 126.0, 126.1,
126.5, 126.8, 127.3, 127.7, 127.8, 127.9, 127.94, 128.0, 128.1, 128.2,
128.26, 128.3, 128.4, 128.6, 131.0, 131.1, 131.4, 131.5, 131.9, 132.0,
132.1, 132.2, 132.4, 132.5, 132.53, 132.6, 141.9, 148.2 (Cnaphthyl
ϩ
Cphenyl). Ϫ 31P NMR (CH2Cl2): δ ϭ 16.7 (d, J ϭ 3.6, phosphonate),
27.3 (d, J ϭ 3.6), 27.5 (phosphane oxide). Ϫ C48H41O5P3 (790.8):
calcd. C 72.91, H 5.23, P 11.75; found C 72.66, H 5.48, P 11.46.
Experimental Section
General: All operations were carried out excluding air and moisture
(R)-(؉)-4,4Ј-Bis(diethoxyphosphoryl)-2,2Ј-bis(diphenylphosphoryl)-
1,1Ј-binaphthyl (5): Crude 3 (2.00 g containing 2.1 mmol of 3), di-
ethyl phosphite (1.22 g, 10 mmol), tetrakis(triphenylphosphane)-
palladium (0.58 g, 0.5 mmol) and triethylamine (1.11 g, 11 mmol)
were dissolved in absolute toluene (5 mL) and stirred for 40 hours
at 90 °C. Then the solution was treated in the same manner as
described above for the solution of 4. After chromatography 5 was
isolated as a glassy mass. Ϫ Yield: 1.03 g (53%). Ϫ MS: (m/z) ϭ
927 [Mϩ ϩ 1]. Ϫ [α]2D0 ϭ ϩ157.9 (CHCl3, c ϭ 1.0). Ϫ 1H NMR
([D6]DMSO): δ ϭ 1.25, 1.35 (2m, 12 H, CH3), 4.03Ϫ4.29 (3m, 8
H, CH2), 6.63 (d, J ϭ 8.2, 2 H, HD), 6.69 (dt, J ϭ 6.8, 1.0, 2 H,
HC), 7.18Ϫ7.39 (m, 14 H, Hphenyl), 7.44 (m, 4 H, HBϩHphenyl), 7.79
(dd, J ϭ 12.5, 4 H, Hphenyl, 7.3), 8.04 (dd, J ϭ 16.5, 11.6, 2 H, HF),
8.59 (d, J ϭ 8.5, 2 H, HA). Ϫ 13C NMR ([D6]DMSO): δ ϭ 15.9,
16.0 (2d, J ϭ 3.1, CH3), 62.1, 62.3 (2d, J ϭ 5.8, CH2), 124.4 (dd,
J ϭ 172.8, 11.3), 126.2, 126.3, 126.7, 126.9, 128.3, 128.4, 128.5,
128.5 (dd, J ϭ 87.0, 14.3), 128.9, 130.5, 131.2, 131.3, 131.7, 131.8,
132.0, 132.2, 132.5 (m), 133.2 (m), 134.8, 146.6. Ϫ 31P NMR
(CH2Cl2): δ ϭ 16.4 (d, J ϭ 4.6, phosphonate), 27.1 (d, J ϭ 4.6,
phosphane oxide). Ϫ C52H50O8P4 (926.9): calcd. C 67.38, H 5.44,
P 13.37; found C 67.70, H 5.56, P 13.59.
under an atmosphere of argon. Solvents were dried with sodium
˚
wire (toluene), molecular sieves 4 A (dichloromethane) or distilled
in an argon stream with LiAlH4 (ethers). Solvents were deoxygen-
ated before use by repeated evacuation and argon purging. NMR
spectra were recorded on a Varian UNITYPLUS 300 or 500 (300
and 500 MHz). Chemical shifts are given in ppm with respect to
TMS (1H, 13C) or H3PO4 (31P), coupling constants are reported
in Hz. Optical rotations were measured on a PerkinϪElmer 241
polarimeter. Mass spectra were obtained on an Autospec (Microm-
ass). Elemental analyses were determined with an Optima 3000 XL
(PerkinϪElmer) and an EA 1110 (CE Instruments). It was difficult
to obtain reliable elemental analyses for the air-sensitive com-
pounds 6؊9. As an alternative LSI-MS spectra were recorded. (R)-
BINAP oxide (1) was prepared according to a literature method.[17]
(R)-4-Bromo-2,2Ј-bis(diphenylphosphoryl)-1,1Ј-binaphthyl (2), (R)-
4,4Ј-dibromo-2,2Ј-bis(diphenylphosphoryl)-1,1Ј-binaphthyl (3): Com-
pound 1 (15.06 g, 23 mmol) was dissolved in CH2Cl2 (340 mL).
While the solution was stirred, Br2 (11.03 g, 69 mmol) and pyridine
(1.82 g, 23 mmol) were added. The stirring was continued at room
temperature for 20 hours. Thereafter the organic phase was ex-
tracted with 1  aqueous sodium hydrogen sulfite (320 mL), brine
and saturated sodium hydrogen carbonate solution. Drying over
(R)-(؉)-4-Diethoxyphosphoryl-2,2Ј-bis(diphenylphosphanyl)-1,1Ј-
binaphthyl (6): Compound 4 (1.88 g, 2.38 mmol) and phenylsilane
Eur. J. Org. Chem. 2001, 477Ϫ481
479

M. Kant, S. Bischoff, R. Siefken, E. Gründemann, A. Köckritz
SHORT COMMUNICATION
(10 mL) were refluxed for 60 h. The silane was removed in vacuo
and the foamy residue was chromatographed on silica gel (eluent:
ethyl acetate/hexane, 1:2) giving a glassy oil. Ϫ Yield: 1.15 g (64%).
Ϫ MS: (m/z) ϭ 759 [Mϩ ϩ 1]. Ϫ [α]2D0 ϭ ϩ84.9 (DMSO, c ϭ 1.0).
Ϫ 1H NMR (CDCl3): δ ϭ 1.17, 1.18 (2t, 6 H, CH3), 3.90Ϫ4.10 (m,
4 H, CH2), 6.66 (d, J ϭ 8.3, 1 H), 6.74Ϫ6.86 (m, 3 H), 6.92Ϫ7.12
(m, 20 H), 7.26 (t, J ϭ 8.3, 1 H), 7.35 (m, 2 H), 7.74 (d, J ϭ 7.8,
1 H), 7.82 (d, J ϭ 8.8, 1 H), 7.90 (d, J ϭ 16.6, 1 H), 8.54 (d, J ϭ
8.8, 1 H, CHnaphthyl ϩ CHphenyl). Ϫ 13C NMR (CDCl3): δ ϭ 15.2,
15.3 (CH3), 61.3, 61.5 (2d, J ϭ 6.1, CH2), 123.9 (d, J ϭ 184.3),
125.0, 125.2, 125.6, 126.1, 126.6, 126.7, 126.9, 127.0, 127.1, 127.2,
127.3, 127.4, 127.5, 127.6, 129.4, 131.5, 131.6, 131.7, 131.8, 131.9,
132.0, 132.2, 132.6 (m), 132.9, 133.0, 133.2, 133.3, 133.5, 133.6,
133.8 (m), 134.4 (d, J ϭ 8.2), 135.6 (m), 136.2 (d, J ϭ 6.1), 136.4
130.1, 130.3, 130.6 (m), 131.2, 135.1 (m), 135.8 (m), 136.5 (m),
138.9 (m), 139.6 (m), 151.5 (m). Ϫ 31P NMR: δ ϭ 14.4 (phosphonic
acid), Ϫ15.7 (phosphane).
Acknowledgments
The authors thank the German Federal Ministry of Education and
Research (BMBF) for the financial support of this work. Mrs. S.
Ziemann, Mrs. R. Bienert and Mrs. H. Gehrmann are gratefully
acknowledged for their technical assistance.
(d, J ϭ 10.1), 136.8 (m), 138.2, 143.3 (m), 149.4 (m, Cnaphthyl
ϩ
Cphenyl). Ϫ 31P NMR (acetone/hexane, 1:1): δ ϭ 17.4 (phosphon-
ate), Ϫ14.6 (dd, J ϭ 29.0, 15.3, phosphane).
M. Beller, B. Cornils, C. D. Frohning, C. W. Kohlpaintner, J.
Mol. Cat. A: Chem. 1995, 104, 17Ϫ85.
[1]
[2]
B. Cornils, W. A.,Herrmann, R. W. Eckl, J. Mol. Cat. A: Chem.
(R)-(؉)-4,4Ј-Bis(diethoxyphosphoryl)-2,2Ј-bis(diphenylphosphanyl)-
1,1Ј-binaphthyl (7): Compound 5 (0.93 g, 1 mmol) and phenylsilane
(6 mL) were refluxed for 65 h. The mixture was cooled down and
kept in the refrigerator overnight. Colourless crystals precipitated.
These were filtered off, washed with n-hexane and dried in vacuo.
Ϫ Yield: 0.50 g (56%). Ϫ m.p.: 221Ϫ224 °C. Ϫ MS: (m/z) ϭ 895
[Mϩ ϩ 1]. Ϫ [α]2D0 ϭ ϩ102.6 (CH2Cl2, c ϭ 1.0). Ϫ 1H NMR
(CDCl3): δ ϭ 0.89, 0.93 (2t, 12 H, CH3), 3.63Ϫ4.26 (3m, 8 H, CH2)
6.68 (d, J ϭ 8.5, 2 H), 6.82 (dt, J ϭ 8.1, 1.3, 2 H), 7.37 (dt, J ϭ
8.1, 1.3, 2 H), 7.90 (dd, J ϭ 16.6, 2.1, 2 H), 8.55 (d, J ϭ 8.5, 2 H,
CHnaphthyl), 6.91Ϫ6.94 (m, 2 H), 7.01Ϫ7.07 (m, 4 H), 7.11Ϫ7.15
(m, 4 H, CHphenyl). Ϫ 13C NMR (CDCl3): δ ϭ 16.2, 16.3 (CH3),
62.4, 62.6 (2d, J ϭ 6.0), 124.4 (d, J ϭ 184.1), 126.4, 126.7 (d, J ϭ
4.5), 127.9, 128.0, 128.1, 128.3 (t, J ϭ 3.9), 128.4 (t, J ϭ 2.5), 128.8,
128.9, 130.9, 132.5, 132.7 (m), 134.4 (m), 135.9 (m), 137.2 (m),
149.5 (m, Cnaphthyl ϩ Cphenyl). Ϫ 31P NMR (CH2Cl2): δ ϭ 17.3
(phosphonate), Ϫ15.0 (phosphane).
1997, 116, 27Ϫ33.
[3]
B. Cornils, J. Mol. Cat. A: Chem. 1999, 143, 1Ϫ10.
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601, 138Ϫ141.
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327Ϫ334.
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[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
(R)-(؉)-2,2Ј-Bis(diphenylphosphanyl)-4-phosphono-1,1Ј-binaphthyl
(8): Compound 6 (1.00 g, 1.31 mmol) was stirred with bromotrime-
thylsilane (5 mL) at room temperature for 24 hours. Then volatile
components were evaporated in vacuo and the residue was dis-
solved in a mixture of THF (5 mL) and water (2 mL), stirred for
1 h and concentrated in vacuo. A dry foam of 8 resulted. Ϫ Yield:
[13]
[14]
[15]
0.92 g (quantitative). Ϫ MS: (m/z) ϭ 703 [Mϩ ϩ 1]. Ϫ [α]2D0
ϭ
[16]
1
ϩ92.4 (DMSO, c ϭ 1.0). Ϫ H NMR (CD3OD): δ ϭ 6.53 (d, J ϭ
8.5, 1 H), 6.69 (d, J ϭ 8.2, 1 H), 6.75 (dt, J ϭ 7.9, 1.3, 1 H), 6.80
(t, J ϭ 7.2, 1 H), 7.24 (dt, J ϭ 8.2, 1.3, 1 H), 7.29 (dd, J ϭ 8.8,
2.8, 1 H), 7.31 (dt, J ϭ 8.0, 1.5, 1 H), 7.76 (d, J ϭ 8.1, 1 H), 7.81
(d, J ϭ 8.5, 1 H), 8.13 (dd, J ϭ 16.2, 1.6, 1 H), 8.61 (d, J ϭ 8.5, 1
H), 6.90Ϫ7.11 (m, 20 H). Ϫ 13C NMR (CD3OD): δ ϭ 128.0, 128.7
(d, J ϭ 156.2), 128.9, 129.4, 130.0 (m), 130.2 (m), 130.3Ϫ130.5 (m),
130.9, 131.0, 132.7, 135.0 (m), 135.2 (m), 136.3, 136.5, 136.6, 136.7.
[17]
D. Cai, J. F. Payack, D. R. Bender, D. L. Hughes, T. R. Ver-
hoeven, P. J. Reider, J. Org. Chem. 1994, 59, 7180. To obtain
the BINAP oxide 1 BINAP prepared by this procedure was
oxidized subsequently with H2O2/EtOH: BINAP (22.42 g,
36 mmol) was suspended in acetone (700 mL) and H2O2 (8 mL,
82 mmol) was added. Stirring was continued overnight and
H2O (300 mL) was added slowly. The colourless precipitate was
collected by filtration and dried. Yield 15.7 g (67%), m.p.
261Ϫ263 °C (ref.[28] 256Ϫ258 °C), [α]2D5 ϭ ϩ385.1 (c ϭ 0.514,
benzene) (ref.[28] [α]2D5 ϭ ϩ388).
Ϫ
31P NMR (DMSO): δ ϭ 11.8 (phosphonic acid), Ϫ16.3 (dd, J ϭ
[18]
64.1, 9.2, phosphane); [(S)-(Ϫ)-phenyl ethylamine]: δ ϭ6.4 (phos-
phonic acid salt), Ϫ15.0 (d, J ϭ 4.6), Ϫ16.4 (d, J ϭ 6.1, phos-
phane).
S. Akutagawa, Appl. Cat. A: General 1995, 128, 171Ϫ207.
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J. P. Coleman, Chem. Ind. (Dekker) 1994, 53, 49Ϫ68.
K. Wan, M. E. Davies, J. Chem. Soc., Chem. Commun. 1993,
1262Ϫ1264.
H. Ding, J. Kang, B. E. Hanson, C. W. Kohlpaintner, J. Mol.
Cat. A: Chem. 1997, 124, 21Ϫ28.
[19]
[20]
(R)-(؉)-2,2Ј-Bis(diphenylphosphanyl)-4,4Ј-bisphosphono-1,1Ј-
binaphthyl (9): Compound 7 (2.00 g, 2.23 mmol) was subjected to
the same procedure as described above for 6. Ϫ Yield: 1.74 g
(quantitative). Ϫ MS: (m/z) ϭ 782 [Mϩ]. Ϫ [α]2D0 ϭ ϩ92.4 (DMSO,
[21]
[22]
Q.-H. Fan, G.-J. Deng, X.-M. Chen, W.-C. Xie, D.-Z. Jiang,
D.-S. Liu, A. S. C. Chan, J. Mol. Cat. A: Chem. 2000, 159,
1
c ϭ 1.0). Ϫ H NMR (CD3OD): δ ϭ 6.64 (d, J ϭ 8.5, 2 H), 6.80
37Ϫ43.
(dt, J ϭ 8.1, 1.3, 2 H), 7.34 (dt, J ϭ 8.1, 1.3, 2 H), 8.15 (d, J ϭ
16.2, 2 H), 8.62 (d, J ϭ 8.5, 2 H, CHnaphthyl), 6.96Ϫ6.99 (m, 8 H),
7.02Ϫ7.08 (m, 10 H), 7.11 (t, J ϭ 7.2, 7.3, 2 H, CHphenyl). Ϫ 13C
NMR (CD3OD): δ ϭ 129.1 (d, J ϭ 163.5), 129.6 (d, J ϭ 4.6),
[23]
D. Hoegaerts, P.A. Jacobs, Tetrahedron: Asymmetry 1999, 10,
3039Ϫ3043.
T. Hirao, T. Masunaga, Y. Ohshiro, T. Agawa, Synthesis
1981, 56Ϫ57.
[24]
480
Eur. J. Org. Chem. 2001, 477Ϫ481

4- and 4,4Ј-Phosphorylated 2,2Ј-Bis(diphenylphosphanyl)-1,1Ј-binaphthyls
SHORT COMMUNICATION
[25]
J. Gloede, S. Ozegowski, A. Köckritz, I. Keitel, Phosphorus,
Lappe, D. Peters, D. Regnat, W. A. Herrmann, J. Mol. Cat. A:
Chem. 1997, 116, 49Ϫ53.
Sulfur, and Silicon 1997, 131, 141Ϫ145.
[26]
[27]
In the phosphane oxide PhP(O)[3-P(O)(OH)2-C6H4]2,[16] where
the hydrogen in the 2-position of the phosphonic acid-substi-
tuted ring can be compared with HE in 5, JPCCH ϭ 11.7 and
8.2 Hz.
[28]
H. Takaya, S. Akutagawa, R. Noyori, Org. Synth. 1988, 67,
20Ϫ31.
Received September 7, 2000
[O00461]
H. Bahrmann, H. Bach, C. D. Frohning, H. J. Kleiner, P.
Eur. J. Org. Chem. 2001, 477Ϫ481
481