Sulfonated diphenylphosphanes for homogeneous biphasic catalysis via a combined protection/deprotection protocol

Article abstract of DOI:10.1002/1099-0690(200108)2001:15<2923::AID-EJOC2923>3.0.CO;2-I

Oxidation of the sulfonated oxygen-labile alkyl- and benzyldiphenylphosphanes 3a-f during hydrolytic workup of the oleum-containing sulfonation mixture is prevented by "soft" hydrolysis with disodium oxalate or basic aluminum oxide. Furthermore, the use o

Full text of DOI:10.1002/1099-0690(200108)2001:15<2923::AID-EJOC2923>3.0.CO;2-I

FULL PAPER
Sulfonated Diphenylphosphanes for Homogeneous Biphasic Catalysis via a
Combined Protection/Deprotection Protocol
Helge Jänsch,[a] Sven Kannenberg,[a] and Gernot Boche*[a]
Keywords: P ligands / Water chemistry / Sulfur / Biphasic catalysis
Oxidation of the sulfonated oxygen-labile alkyl- and
benzyldiphenylphosphanes 3a−f during hydrolytic workup of ane adducts 6a−f for storage and purification purposes. De-
the oleum-containing sulfonation mixture is prevented by
protection yields the corresponding sulfonated alkyl- and
for the synthesis of the air-stable sulfonated phosphanylbor-
‘‘soft’’ hydrolysis with disodium oxalate or basic aluminum benzyldiphenylphosphanes 7a−f.
oxide. Furthermore, the use of a protection protocol allows
Introduction
benzyldiphenylphosphanes 1aϪf in degassed concentrated
sulfuric acid (96%) protonation to 2aϪf protected the phos-
phorus atom from oxidation (see Scheme 1). This is evi-
denced by a large upfield shift of the phosphorus singlet by
approximately 20Ϫ30 ppm (see Table 1). As a consequence,
the addition of oleum (65%) to the reaction mixture at 0 °C
did not lead to oxidation of the phosphorus atom. In order
to assure complete sulfonation to 3aϪf, the reaction mix-
ture was kept at 30Ϫ50 °C for 2 days.
Water-soluble phosphane ligands form transition metal
complexes which serve as catalysts in biphasic industrial
processes.[1] Several routes towards the synthesis of sulfon-
ated phosphanes have been described in the literature. How-
ever, these procedures are often unreliable or tedious.
In the course of our investigations of Pd-catalyzed bi-
phasic aromatic aminations[2] we attempted to prepare new
water-soluble phosphane ligands by sulfonation. Following
literature procedures we were challenged by considerable
oxidation of the oxygen-labile phosphanes. Neither direct
sulfonation with concentrated sulfuric acid and oleum in
varying ratios and at different temperatures,[3] nor Herr-
mann’s boric acid protocol[4] turned out to be satisfactory.
Alkylphosphanes, with the exception of ethyldiphenylphos-
phane (1b), were oxidized at phosphorus in different
amounts, while benzyldiphenylphosphane (1f) could not be
sulfonated without complete oxidation when using the di-
rect route. Attempts to prepare a sulfonated DPEphos-ana-
logue[5] with boric acid/sulfuric acid/oleum resulted in phos-
phane oxidation of at least 30%. Following Larpent’s strat-
egy of silver-mediated esterification of sulfonated phos-
phane oxides followed by trichlorosilane reduction and
deesterification,[6] we found that the esterification step gives
results that are difficult to reproduce, while the reduction
of sterically congested sulfonated phosphane oxides (e.g.
sulfonated diphenyl-tert-butylphosphane oxide) did not
proceed to completion.
Scheme 1
Table 1. 31P NMR chemical shifts of 1 and 2
Substance
1 (δ [ppm], CDCl3)
2 (δ [ppm], D2O)
a
b
c
d
e
f
Ϫ26.3
Ϫ
Ϫ15.1
18.3
Ϫ3.2
Ϫ9.3
5.5
13.2
12.7
32.0
19.9
16.8
We describe here a new method for the synthesis of sul-
fonated alkyl- and benzyldiphenylphosphane ligands via P-
protected sulfonated tertiary phosphanes.
Substantial oxidation at phosphorus of the more labile
3aϪf occurred, however, during dropwise hydrolysis on
crushed ice. In order to minimize this undesired reaction we
added the reaction solution containing 3aϪf at low temper-
ature (Ϫ78 °C) to the salts of various acids, some of which
possess reducing properties. After the addition of water and
warming to room temperature, magnesium oxide (MgO),
sodium carbonate (Na2CO3) or sodium formate (HCO2Na)
yielded a mixture of sulfonated phosphanes and the corres-
ponding phosphane oxides, as judged by 31P NMR spectro-
Results and Discussion
Monitoring the direct sulfonation reaction by 31P NMR
spectroscopy we found that after dissolution of the alkyl- or
[a]
Philipps-Universität, Fachbereich Chemie
35032 Marburg, Germany
E-mail: boche@chemie.uni-marburg.de
Eur. J. Org. Chem. 2001, 2923Ϫ2926
WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
1434Ϫ193X/01/0815Ϫ2923 $ 17.50ϩ.50/0
2923

H. Jänsch, S. Kannenberg, G. Boche
FULL PAPER
scopy. With disodium oxalate (Na2C2O4) or basic alumi- addition of methanol/ethanol afforded the p,m,m isomer,
num oxide (Al2O3), however, no or only little oxidation of even though traces of a second compound with identical
phosphorus was observed. Since the use of HCO2Na, being splitting of signals, but slightly different shifts was de-
a reducing agent, leads also to oxidation at phosphorus, tected, too.
which is not the case with Al2O3, we do not attribute the
The deprotection of the borane/phosphane adducts 6aϪf
observed minimized oxidation in the presence of Na2C2O4 was achieved by heating with allyl alcohol in water
to its reducing power. While the reaction of the earlier men- (Scheme 3).[9] After extraction with 1-butanol and separa-
tioned salts (Na2CO3, MgO, HCO2Na) with the reaction tion of the phases the sulfonated phosphanes 7aϪf re-
mixture to give mixed sulfuric acid anhydrides is exothermic mained in the aqueous layer. Deprotection was complete,
(vide infra), the reaction with Na2C2O4 or basic Al2O3 is and only traces of oxidation at phosphorus were observed
less so. Thus we assume the heat formation in this case to (see Table 3).
be lower than for direct hydrolysis on ice, resulting in less
oxidation of phosphorus by SO3.
Following the procedure described by Herrmann et al.
the sulfonic acids 4aϪf were then extracted into toluene
with triisooctylamine (TIOA; Scheme 2).[4] The depro-
tonated sulfonated alkyl- and benzylphosphanes 5aϪf can
easily be protected with BH3 for storage by the reaction
with BH3·SMe2, yielding the corresponding borane
adducts 6aϪf after reextraction of the organic layer with
sodium hydroxide solution (Scheme 2).[7] Subsequent dry-
ing affords the protected phosphanes 6aϪf as air-stable
solids in acceptable yields (see Table 2). During the reex-
traction step the phosphane oxides can be separated by re-
Scheme 3
peated addition of small amounts of sodium hydroxide so-
lution, as phosphane oxides are more water-soluble than
the corresponding borane adducts. Nonprotected sulfo-
Table 3. Yields of 7aϪf from 6aϪf
nated phosphanes can readily be obtained for immediate
use by identical workup, except for protection.
Substance
7 (%)
P-oxide of 7 (%)
In the case of the trisulfonated benzyldiphenylphos-
phane 6f, the o,m,m isomer was detected as well as the
p,m,m isomer.[8] Recrystallisation from water by stepwise
a
b
c
d
e
f
80
93
86
80
82
89
5.0
6.4
7.0
5.5
2.7
7
Conclusions
We have presented a new and convenient route to water-
soluble phosphane ligands. Oxidation of phosphorus by
SO3 that is possibly attributable to the heat of hydrolysis of
pyrosulfuric acid in the reaction medium is circumvented by
‘‘soft’’ hydrolysis using disodium oxalate or basic aluminum
oxide. Sulfonated alkyl- and benzyldiphenylphosphanes are
accessible as their air-stable borane adducts 6aϪf. Further
purification, storage and handling in the solid state, as well
as in solution, is easily achieved. Deprotection occurs under
mild conditions to give the desired, unprotected sulfonated
phosphanes 7aϪf.
The ligands 7aϪf mentioned above form complexes with
palladium acetate that are catalytically active in Heck reac-
tions. Evaluation of their reactivity in view of their elec-
tronic and structural properties in biphasic catalytic aryl-
aminations and Heck reactions is under way and will be
communicated soon. Further work is aimed at the prepara-
tion of bidentate sulfonated phosphane ligands.
Scheme 2
Table 2. Yields of 6aϪf
Substance
6 (%)
P-oxide of 6 (%)
a
b
c
d
e
f
65
65
67
69
64
5[a]
1.0
0.4
Ϫ
0.4
3.9
Ϫ
[a]
56 mg after crystallization from water/methanol. A further
432 mg were isolated as a mixture of o,m,m and p,m,m isomers
from the mother liquor
2924
Eur. J. Org. Chem. 2001, 2923Ϫ2926

Sulfonated Diphenylphosphanes for Homogeneous Biphasic Catalysis
FULL PAPER
Disodium Salt of the Bis(m-sulfonatophenyl)methylphosphaneborane
adduct (6a): H NMR (200 MHz, D2O): δ ϭ 0.00Ϫ1.65 (br. m, 3
Experimental Section
1
2
3
H, BH3), 1.79 (d, JH,P ϭ 10.8, 3 H, HMe), 7.39 (ddd, JH3,H4
ϭ
General: The reagents mentioned in the experimental procedures
are commercially available and were used without further purifica-
tion. Solvents were degassed and dried by standard techniques. Pre-
parations were carried out employing standard Schlenk techniques.
The progress of the reactions was determined by 31P NMR
spectroscopy. NMR spectra were recorded on Bruker spectrometers
ARX-200 MHz, AC-300 MHz, DRX-400 MHz and AMX-
500 MHz, respectively. H3PO4 was used as an external standard for
the 1H-decoupled 31P NMR measurements. CDCl3 in a separate
reservoir served as an external standard for the 13C spectra of
water-soluble compounds. Coupling constants are quoted in Hz.
Mass spectra were determined on a Varian MAT CH7a (EI), a
Hewlett Packard Series 1100MSD (ESI) or a Micromass Ltd.
Autospec (HRMS) mass spectrometer. For atom labeling see
Scheme 3.
3
4
3
7.5, JH3,H2 ϭ 7.8, JH,P ϭ 2.0, 2 H, H3), 7.55 (dd, JH,P ϭ 10.5,
3JH2,H3 ϭ 9.0, 2 H, H2), 7.77 (dd, JH4,H3 ϭ 8.0, JH,? ϭ 1.3, 2 H,
3
H4), 7.93 (d, 3JH,P ϭ 11.0, 2 H, H6). Ϫ 13C NMR (100 MHz): δ ϭ
1
1
9.6 (d, JC,P ϭ 41.0, CMe), 130.5 (d, JC,P ϭ 56.8, C1), 128.4 (d,
2JC,P ϭ 11.1, C6), 128.6 (s, C4), 129.9 (d, JC,P ϭ 9.8, C3), 134.5
3
(d, JC,P ϭ 9.0, C2), 143.3 (d, JC,P ϭ 10.2, C5). Ϫ 31P NMR
(81 MHz, D2O): δ ϭ 13.6 (br. s, P). Ϫ MS (ESI, neg. mode): m/z
(%) ϭ 395 (18) [M Ϫ Naϩ], 179 (100) [M Ϫ 2NaϩϪBH3]. Ϫ
HRMS (ESI, neg. mode): calculated for C13H11NaO6PS2:
380.9647; found 380.9632.
2
3
Disodium Salt of the Bis(m-sulfonatophenyl)ethylphosphaneborane
1
Adduct (6b): H NMR (200 MHz, D2O): δ ϭ 0.00Ϫ0.18 (br. m, 3
3
3
H, BH3), 0.84 (dt, JH,P ϭ 18.5, JH,H ϭ 7.5, 3 H, HMe), 2.19 (dq,
2JH,P ϭ 11.3, JH,H ϭ 7.3, 2 H, Halkyl), 7.39 (ddd, JH3,H4 ϭ 7.5,
3
3
3JH3,H2 ϭ 7.8, JH,P ϭ 2.0, 2 H, H3), 7.55 (dd, JH,P ϭ 9.0,
4
3
The alkyldiphenylphosphanes (1aϪf) were prepared by published
methods or slight modifications thereof:[10] diphenylmethylphos-
phane (1a; see ref.[11]); diphenylethylphosphane (1b; purchased
from Aldrich and employed without further purification); n-Butyl-
diphenylphosphane (1c; see ref.[12]); diphenyl-tert-butylphos-
phane (1d; see ref.[13]); cyclohexyldiphenylphosphane (1e; see
ref.[13]); benzyldiphenylphosphane (1f; see refs.[13,14]).
3JH2,H3 ϭ 8.8, 2 H, H2), 7.74 (d, JH4,H3 ϭ 7.8, 2 H, H4), 7.88 (d,
3
3JH,P ϭ 10.3, 2 H, H6). Ϫ 13C NMR (125 MHz): δ ϭ 6.5 (s, CMe),
1
2
17.4 (d, JC,P ϭ 40.0, Calkyl), 128.9 (s, C4), 129.1 (d, JC,P ϭ 14.4,
C6), 129.6 (d, JC,P ϭ 54.8, C1), 130.2 (d, JC,P ϭ 9.5, C3), 135.2
1
3
(d, JC,P ϭ 8.4, C2), 143.6 (d, JC,P ϭ 10.1, C5). Ϫ 31P NMR
(81 MHz, D2O): δ ϭ 21.9 (br. s, P). Ϫ MS (ESI, neg. mode): m/z
(%) ϭ 409 (26) [M Ϫ Naϩ], 193 (51) [M Ϫ 2Naϩ], 186 (100) [M Ϫ
2Naϩ Ϫ BH3].
2
3
Typical Procedure for the Preparation of Sulfonated Alkyl- or
Benzyldiphenylphosphaneborane
Adducts (6aϪf):
Diphenyl-
phosphane 1aϪf (10 mmol) was dissolved in 5 mL of degassed,
concentrated sulfuric acid (96%) at 0 °C under an inert gas atmo-
sphere. After complete dissolution of the phosphane, 5 mL of
oleum (65%) was added to the cooled mixture. The reaction mix-
ture was then warmed to 50 °C for 48 h. In the case of benzyl-
diphenylphosphane (1f) the reaction mixture was warmed to 30 °C
for 48 h]. After cooling to room temperature 2 mL of the reaction
mixture was slowly added to 2 g (15 mmol) of Na2C2O4) or 2 g of
Al2O3 (aluminum oxide for chromatography, basic) at Ϫ78 °C un-
der an inert atmosphere. After warming to room temperature the
suspension was stirred in vacuo for 10 min. before cooling to Ϫ78
°C. Then 10 mL of degassed water was added and after 20 min.
the reaction vessel was warmed to room temperature. The solids
were filtered off and the liquid phase was overlaid with 10 mL of
toluene. 2 mL (4.06 mmol) of TIOA was then added and the mix-
ture was stirred for 30 min. The organic layer was separated and
washed twice with 5 mL of degassed water before 1 mL
(2.00 mmol) BH3·SMe2 (2  in THF) was added. After evolution
of SMe2 had ceased the reaction mixture was washed three times
with 20 mL of water. Then, 10 mL of water and 0.4 mL
(4.00 mmol) of 10  sodium hydroxide were added and the biphasic
solution was mixed thoroughly. The separated aqueous phase was
evaporated under reduced pressure and the remaining residue dried
in vacuo. In the case of benzyldiphenylphosphane 1f 3 mL
(6.09 mmol) TIOA, 1.5 mL (3.00 mmol) BH3·SMe2 (2  in THF)
and 0.6 mL (6.00 mmol) of 10  sodium hydroxide were added].
Disodium Salt of the Bis(m-sulfonatophenyl)-n-butylphosphaneborane
Adduct (6c): H NMR (200 MHz, D2O): δ ϭ 0.20Ϫ1.80 (br. m, 3
H, BH3), 0.60 (m, 3 H, HMe), 1.16 (m, 4 H, Halkyl), 2.18 (m, 2 H,
1
3
3
4
Halkyl), 7.41 (ddd, JH3,H4 ϭ 7.5, JH3,H2 ϭ 7.8, JH,P ϭ 1.8, 2 H,
3
3
H3), 7.59 (dd, JH,P ϭ 9.8, JH2,H3 ϭ 8.3, 2 H, H2), 7.78 (d,
3JH4,H3 ϭ 7.5, 2 H, H4), 7.94 (d, JH,P ϭ 10.5, 2 H, H6). Ϫ 13C
3
1
NMR (100 MHz): δ ϭ 12.7 (s, CMe), 23.2 (d, JC,P ϭ 37.8, Calkyl),
23.3 (d, JC,P ϭ 14.2, Calkyl), 24.5 (s, Calkyl), 128.6 (s, C4), 128.9 (d,
2JC,P ϭ 10.7, C6), 129.7 (d, 1JC,P ϭ 50.2, C1), 129.9 (d, 3JC,P ϭ 9.6,
2
3
C3), 134.8 (d, JC,P ϭ 8.3, C2), 143.4 (d, JC,P ϭ 10.2, C5). Ϫ 31P
NMR (81 MHz, D2O): δ ϭ 19.6 (br. s, P). Ϫ MS (ESI, neg. mode):
m/z (%) ϭ 437 (21) [M Ϫ Naϩ], 200 (100) [M Ϫ 2Naϩ Ϫ BH3].
Disodium Salt of the Bis(m-sulfonatophenyl)-tert-butylphosphanebor-
ane Adduct (6d): 1H NMR (200 MHz, D2O): δ ϭ 0.20Ϫ1.60 (br. m,
3
3
3 H, BH3), 1.02 (d, JH,P ϭ 15.0, 9 H, HtBu), 7.44 (dd, JH3,H4
ϭ
7.8, JH3,H2 ϭ 7.8, 2 H, H3), 7.71 (dd, 3JH,P ϭ 8.8, 3JH2,H3 ϭ 8.8, 2
3
3
3
H, H2), 7.80 (d, JH4,H3 ϭ 7.8, 2 H, H4), 8.05 (d, JH,P ϭ 10.0, 2
H, H6). Ϫ 13C NMR (125 MHz): δ ϭ 26.0 (s, CtBu), 30.7 (d, 1JC,P ϭ
1
31.3, Cquart), 127.9 (d, JC,P ϭ 51.3, C1), 128.6 (s, C4), 129.6 (d,
3JC,P ϭ 8.9, C3), 130.5 (d, JC,P ϭ 9.8, C6), 136.5 (d, JC,P ϭ 6.9,
2
2
C2), 143.1 (d, JC,P ϭ 10.0, C5). Ϫ 31P NMR (81 MHz, D2O): δ ϭ
3
35.6 (br. s, P). Ϫ MS (ESI, neg. mode): m/z (%) ϭ 437 (30) [M Ϫ
Naϩ], 207 (95) [M Ϫ 2Naϩ], 200 (100) [M Ϫ 2Naϩ Ϫ BH3].
Disodium Salt of the Bis(m-sulfonatophenyl)cyclohexylphosphane-
borane Adduct (6e): 1H NMR (200 MHz, D2O): δ ϭ 0.30Ϫ1.50 (m,
3
Typical Procedure for the Deprotection of Sulfonated Alkyl- or 13 H, HCy,BH3), 2.47 (br. m, 1 H, HCy), 7.36 (dd, JH3,H2 ϭ 7.3,
Benzyldiphenylphosphanylboranes (6aϪf): 100 mg of sulfonated 3JH3,H4 ϭ 7.5, 2 H, H3), 7.63 (dd, JH,P ϭ 9.0, JH2,H3 ϭ 8.3, 2 H,
3
3
3
3
phosphane/borane adduct 6aϪf was dissolved in 5 mL of degassed
water. After the addition of 1 mL (14.6 mmol) of degassed allyl
H2), 7.75 (d, JH4,H3 ϭ 7.8, 2 H, H4), 7.96 (d, JH,P ϭ 10.3, 2 H,
H6). Ϫ 13C NMR (100 MHz): δ ϭ 26.2 (s, CCy), 26.7 (d, JC,P
ϭ
1
alcohol the reaction mixture was stirred at 95 °C for 16 h. The 12.7, CCy), 27.0 (s, CCy), 33.0 (d, JC,P ϭ 35.8, CCy), 129.3 (d,
resulting turbid mixture was cooled to room temperature, 5 mL of 1JC,P ϭ 53.2, C1), 129.5 (s, C4), 130.2 (d, Jc,P ϭ 10.3, C6), 130.6
2
3
2
3
degassed 1-butanol was added, and the biphasic solution was (d, JC,P ϭ 9.1, C3), 135.9 (d, JC,P ϭ 7.5, C2), 144.3 (d, JC,P
ϭ
stirred for 30 min. Separation of the clear aqueous layer, evapora-
tion of the water, and drying in vacuo, yielded the deprotected sul-
fonated alkyl- or benzyldiphenylphosphanes 7aϪf.
9.8; C5). Ϫ 31P NMR (81 MHz, D2O): δ ϭ 24.4 (br. s, P). Ϫ MS
(ESI, neg. mode): m/z (%) ϭ 463 (39) [M Ϫ Naϩ], 220 (100) [M Ϫ
2Naϩ], 213 (97) [M Ϫ 2Naϩ Ϫ BH3].
Eur. J. Org. Chem. 2001, 2923Ϫ2926
2925

H. Jänsch, S. Kannenberg, G. Boche
FULL PAPER
Trisodium Salt of the Bis(m-sulfonatophenyl)-p-sulfonatobenzylphos-
12.2, C1), 142.8 (d, 3JC,P ϭ 7.1, C5). Ϫ 31P NMR (81 MHz, D2O):
δ ϭ Ϫ3.0 (s, P).
phaneborane Adduct (6f): 1H NMR (400 MHz, D2O):
δ ϭ
2
0.30Ϫ1.20 (br. s, 3 H, BH3), 3.81 (d, JH,P ϭ 13.0, 2 H, H7), 7.00
(d, 3JH9,H10 ϭ 7.6, 2 H, H9), 7.49 (dd, 3JH3,H2 ϭ 8.1, 3JH3,H4 ϭ 8.1,
2 H, H3), 7.52 (d, 3JH10,H9 ϭ 7.8, 2 H, H10), 7.66 (dd, 3JH,P ϭ 9.5,
Trisodium Salt of the Bis(m-sulfonatophenyl)-p-sulfonatobenzylphos-
1
phane (7f): H NMR (400 MHz, D2O): δ ϭ 3.42 (s, 2 H), 7.02 (d,
J ϭ 8.6, 2 H), 7.30Ϫ7.40 (m, 4 H), 7.52Ϫ7.54 (d, J ϭ 8.0, 2 H),
7.72Ϫ7.78 (m, 4 H). Ϫ 13C NMR (100 MHz, D2O): δ ϭ 34.1 (d,
J ϭ 13.2), 125.5 (s), 126.4 (s), 129.3 (d, J ϭ 10.9), 129.4 (s), 129.7
(d, J ϭ 6.3), 130.0 (s), 1135.7 (d, J ϭ 18.4), 137.5 (d, J ϭ 14.4),
140.4 (d, J ϭ 6.7), 142.8 (br. s). Ϫ 31P NMR (81 MHz, D2O): δ ϭ
Ϫ5.0 (s, P).
3
3JH2,H3 ϭ 8.6, 2 H, H2), 7.92 (d, JH4,H3 ϭ 7.9, 2 H, H4), 8.03 (d,
3JH,P ϭ 10.9, 2 H, H6). Ϫ 13C NMR (100 MHz): δ ϭ 31.8 (d,
1JC,P ϭ 32.3, C7), 125.2 (s, C9), 125.7 (s, C8), 128.4 (d, 1JC,P ϭ 52.8,
C1), 129.0 (s, C4), 129.2 (d, 2JC,P ϭ 10.2, C6), 129.9 (d, 3JC,P ϭ 9.9,
C3), 130.8 (s, C10), 135.3 (d, 2JC,P ϭ 8.8, C2), 141.2 (s, C11), 143.4
3
(d, JC,P ϭ 9.5, C5). Ϫ 31P NMR (81 MHz, D2O): δ ϭ 211.9 (br.
s, P). Ϫ MS (ESI, neg. mode): m/z (%) ϭ 559 (100) [M Ϫ Naϩ
Ϫ
BH3], 366 (86) [M Ϫ benzyl Ϫ Naϩ]; also 575 [M Ϫ Naϩ Ϫ BH3
ϩ O] in varying amount depending on the fragmentor current.
Acknowledgments
We are grateful to the Fonds der Chemischen Industrie and the
Deutsche Forschungsgemeinschaft, SFB 260, for financial support
of this work. We also would like to thank Dr. Th. Wendrich and
Dipl. Chem. V. Bergendahl of the Fachbereich Chemie, Philipps-
Universität Marburg, for the determination of the ESI mass spec-
tra. Dr. G. Laufenberg of the Fachbereich Pharmazie, Philipps-
Universität Marburg, kindly determined the HRMS.
Disodium Salt of the Bis(m-sulfonatophenyl)methylphosphane (7a):[6]
1H NMR (400 MHz, D2O): δ ϭ 1.60 (d, JH,P ϭ 2.4, 3 H, HMe),
2
3
3
7.40 (dd, 3JH3,H4 ϭ 7.3, JH3,H2 ϭ 8.0, 2 H, H3), 7.44 (dd, JH,P ϭ
7.1, 3JH2,H3 ϭ 7.5, 2 H, H2), 7.72 (d, 3JH4,H3 ϭ 7.3, 2 H, H4), 7.82
(d, JH,P ϭ 7.1, 2 H, H6). Ϫ 13C NMR (100 MHz): δ ϭ 10.6 (d,
3
1JC,P ϭ 10.0, CMe), 125.9 (s, C4), 128.5 (d, 2JC,P ϭ 20.1, C6), 129.3
3
2
1
(d, JC,P ϭ 6.2, C3), 134.9 (d, JC,P ϭ 17.3, C2), 140.2 (d, JC,P
ϭ
11.4, C1), 142.7 (d, 3JC,P ϭ 6.2, C5). Ϫ 31P NMR (81 MHz, D2O):
δ ϭ Ϫ22.5 (s, P).
[1] [1a]
[1b]
E. G. Kuntz, CHEMTECH 1987, 17, 570Ϫ575. Ϫ
B.
Cornils, E. G. Kuntz, J. Organomet. Chem. 1995, 502,
177Ϫ186. Ϫ
[1c]
Disodium Salt of the Bis(m-sulfonatophenyl)ethylphosphane (7b): 1H
N. Yoshimura in Applied Homogeneous Cata-
3
NMR (400 MHz, D2O): δ ϭ 0.87 (dt, 3JH,P ϭ 17.9, JH,H ϭ 7.5, 3
lysis with Organometallic Compounds, (Eds. B. Cornils, W. A.
Herrmann), VCH, Weinheim, 1996, Vol. 1, 351Ϫ358.
G. Wüllner, H. Jänsch, S. Kannenberg, F. Schubert, G. Boche,
Chem. Commun. 1998, 1509Ϫ1510.
3
H, HMe), 1.94 (q, JH,H ϭ 7.5, 2 H, Halkyl), 7.32Ϫ7.38 (m, 4 H,
[2]
3
3
H2,H3), 7.72 (d, JH4,H3 ϭ 7.0, 2 H, H4), 7.80 (d, JH,P ϭ 7.0, 2
H, H6). Ϫ 13C NMR (100 MHz): δ ϭ 9.0 (d, JC,P ϭ 15.1, CMe),
18.9 (d, JC,P ϭ 7.0, Calkyl), 126.0 (s, C4), 129.2 (d, JC,P ϭ 19.8,
2
[3] [3a]
H. C. A. van Lindert, A. Koeberg-Telder, H. Cerfontain,
1
2
[3b]
Recl. Trav. Chim. Pays-Bas 1992, 111, 379Ϫ388. Ϫ
B.
3
2
C6), 129.3 (d, JC,P ϭ 6.2, C3), 135.4 (d, JC,P ϭ 16.6, C2), 138.5
Cornils, P. Lappe, R. Gärtner, H. Springer, EP-A 0107006,
(d, JC,P ϭ 12.1, C1), 142.8 (d, JC,P ϭ 6.4, C5). Ϫ 31P NMR
1
3
1983.
[4] [4a]
(81 MHz, D2O): δ ϭ Ϫ10.2 (s, P).
W. A. Herrmann, G. P. Albanese, R. B. Manetsberger, P.
Lappe, H. Bergmann, Angew. Chem. 1995, 107, 893Ϫ895, An-
[4b]
Disodium Salt of the Bis(m-sulfonatophenyl)-n-butylphosphane (7c):
1H NMR (400 MHz, D2O): δ ϭ 0.97 (m, 3 H, HMe), 1.51 (m, 4 H,
Halkyl), 2.29 (m, 2 H, Halkyl), 7.50 (dd, 3JH3,H2 ϭ 7.7, 3JH3,H4 ϭ 7.7,
gew. Chem. Int. Ed. Engl. 1995, 34, 811Ϫ813. Ϫ
H. Bahr-
mann, K. Bergrath, H. J. Kleiner, P. Lappe, C. Naumann, D.
Peters, D. Regnat, J. Organomet. Chem. 1996, 520, 97Ϫ100. Ϫ
[4c]
3
3
G. P. Albanese, Ph. D. thesis, TU München, 1995.
M. Kranenburg, Y. E. M. van der Burgt, P. C. J. Kamer, P.
2 H, H3), 7.56 (dd, JH,P ϭ 7.0, JH2,H3 ϭ 7.7, 2 H, H2), 7.80 (d,
[5] [5a]
3
3JH4,H3 ϭ 7.7, 2 H, H4), 7.90 (d, JH,P ϭ 6.0, 2 H, H6). Ϫ 13C
W. N. M. van Leeuwen, Organometallics 1995, 14, 3081Ϫ3089.
NMR (100 MHz): δ ϭ 12.9 (s, CMe), 23.4 (d, JC,P ϭ 13.2, Calkyl),
[5b]
Ϫ
M. Kranenburg, J. G. P. Delis, P. C. J. Kamer, P. W. N.
1
25.9 (d, JC,P ϭ 7.4, Calkyl), 27.2 (d, JC,P ϭ 14.0, Calkyl), 126.1 (s,
M. van Leeuwen, K. Vrieze, N. Veldman, A. L. Speck, K. Gou-
bitz, J. Fraanje, J. Chem. Soc., Dalton. Trans. 1997, 1839Ϫ1849.
C. Larpent, H. Patin, N. Thilmont, J. F. Valdor, Synth. Com-
mun. 1991, 21, 495Ϫ503.
2
2
C4), 129.3 (d, JC,P ϭ 26.5, C6), 129.3 (s, C3), 135.5 (d, JC,P
ϭ
1
3
16.8, C2), 138.8 (d, JC,P ϭ 11.7, C1), 142.9 (d, JC,P ϭ 6.4, C5).
[6]
[7]
[8]
Ϫ
31P NMR (81 MHz, D2O): δ ϭ Ϫ14.6 (s, P).
M. Ohff, J. Holz, M. Quirmbach, A. Börner, Synthesis 1998,
1391Ϫ1415.
Disodium Salt of the Bis(m-sulfonatophenyl)-tert-butylphosphane
1
2
(7d): H NMR (200 MHz, D2O): δ ϭ 0.94 (d, JH,P ϭ 13.5, 9 H,
´
T. Bartik, B. Bartik, B. E. Hanson, I. Guo, I. Toth, Organomet-
3
3
H
tBu), 7.31 (dd, JH3,H2 ϭ 7.8, JH3,H2 ϭ 7.8, 2 H, H3), 7.46 (dd,
allics 1993, 12, 164Ϫ170.
3JH,P ϭ 7.0, JH2,H3 ϭ 7.5, 2 H, H2), 7.64 (d, JH4,H3 ϭ 7.8, 2 H,
3
3
[9] [9a]
D. A. Evans, J. Bartoli, T. Godel, Tetrahedron Lett. 1982,
H4), 7.82 (d, JH,P ϭ 7.3, 2 H, H6). Ϫ 13C NMR (50 MHz): δ ϭ
3
23, 4577Ϫ4580. Ϫ [9b] R. A. Braun, D. C. Brown, R. M. Adens,
J. Am. Chem. Soc. 1971, 93, 2823Ϫ2824.
2
1
27.6 (d, JC,P ϭ 13.4, CtBu), 30.4 (d, JC,P ϭ 9.7, Cquart), 126.2 (s,
[10]
3
2
For general procedures see also: V. D. Bianco, S. Doronzo, In-
org. Synth. 1976, 16, 155Ϫ163.
C4), 129.1 (d, JC,P ϭ 6.9, C3), 130.9 (d, JC,P ϭ 20.8, C6), 136.3
(d, 1JC,P ϭ 14.8, C1), 137.3 (d, JC,P ϭ 17.5, C2), 142.5 (d, JC,P ϭ
2
3
[11] [11a]
E. Vincent, L. Verdonck, G. P. Van Der Kelen, J. Mol.
6.9, C5). Ϫ 31P NMR (81 MHz, D2O): δ ϭ 19.5 (s, P).
[11b]
Struct. 1980, 69, 33Ϫ40. Ϫ
E. N. Tsvetkov, N. A. Boudar-
enko, I. G. Malakhova, M. J. Kabachnik, J. Gen. Chem. USSR
1985, 55, 8Ϫ22.
R. J. Bowen, D. Camp, Effendy, P. C. Healy, B. W. Skelton, A.
H. White, Aust. J. Chem. 1994, 47, 693Ϫ701.
S. O. Grim, W. McFarlane, E. F. Davidoff, J. Org. Chem. 1967,
32, 781Ϫ784.
Disodium Salt of the Bis(m-sulfonatophenyl)cyclohexylphosphane
(7e): 1H NMR (500 MHz, D2O): δ ϭ 0.95Ϫ1.04 (m, 3 H, HCy),
1.10Ϫ1.17 (m, 2 H, HCy), 1.46Ϫ1.53 (m, 5 H, HCy), 2.22Ϫ2.28 (m,
[12]
[13]
[14]
3
3
1 H, HCy), 7.36 (dd, JH3,H2 ϭ 7.6, JH3,H4 ϭ 7.8, 2 H, H3), 7.48
3
3
3
(dd, JH2,H3 ϭ 7.3, JH,P ϭ 2 H, H2), 7.69 (d, JH4,H3 ϭ 7.8, 2 H,
H4), 7.83 (d, JH,P ϭ 7.5, 2 H, H6). Ϫ 13C NMR (125 MHz): δ ϭ
3
J. A. van Doorn, N. Meijboom, Recl. Trav. Chim. Pays-Bas
1992, 111, 170Ϫ177.
25.8 (s, CCy), 26.0 (d, JC,P ϭ 12.2, CCy), 29.0 (d, JC,P ϭ 14.2, CCy),
3
34.3 (s, CCy), 126.3 (s, C4), 129.3 (d, JC,P ϭ 6.1, C3), 130.2 (d,
Received February 23, 2001
2
1
2JC,P ϭ 21.4, C6), 136.2 (d, JC,P ϭ 16.3, C2), 136.8 (d, JC,P
ϭ
[O01093]
2926
Eur. J. Org. Chem. 2001, 2923Ϫ2926