Ferrocenyl-aryl based trans-chelating diphosphine ligands: Synthesis, molecular structure and application in enantioselective hydrogenation

Article abstract of DOI:10.1002/adsc.200900906

Potentially trans-chelating diphosphine ligands based on a ferrocenyl-aryl backbone were synthesised in a four-step sequence and the molecular structures in the solid state of two representatives were determined by X-ray diffraction. High throughput screening of these ligands in rhodium-, ruthenium- and iridium-mediated hydrogenations of a variety of alkenes and ketones revealed that these ligands can deliver high enantioselectivity for alkenes (up to 98% ee) but are less selective when ketones are used as the substrates. The coordination behaviour of one ligand in its square planar palladium and platinum dichloride complexes was studied by ³¹P NMR and only trans-chelated complexes, together with oligomeric by-products, were observed. Reaction with the (p-cymene)ruthenium dichloride dimer, [RuCl₂(pcymene)] ₂, resulted in a mixture of diastereomeric complexes.

Full text of DOI:10.1002/adsc.200900906

FULL PAPERS
DOI: 10.1002/adsc.200900906
Ferrocenyl-Aryl Based trans-Chelating Diphosphine Ligands:
Synthesis, Molecular Structure and Application in Enantioselec-
tive Hydrogenation
Raffael Schuecker,a Kurt Mereiter,b Felix Spindler,c,* and Walter Weissensteinera,*
a
Institute of Organic Chemistry, University of Vienna, Wꢀhringer Straße 38, 1090 Wien, Austria
Fax : (+43)-1-4277-9521; e-mail: walter.weissensteiner@univie.ac.at
Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164SC, 1060 Vienna,
b
Austria
c
Solvias AG, Catalysis Research, P.O. Box, 4002 Basel, Switzerland
Received: December 29, 2009; Published online: April 7, 2010
Abstract: Potentially trans-chelating diphosphine li- ligand in its square planar palladium and platinum
gands based on a ferrocenyl-aryl backbone were syn- dichloride complexes was studied by 31P NMR and
thesised in a four-step sequence and the molecular only trans-chelated complexes, together with oligo-
structures in the solid state of two representatives meric by-products, were observed. Reaction with the
were determined by X-ray diffraction. High through- (p-cymene)ruthenium dichloride dimer, [RuCl2ACHTUNGTRENNUNG(p-
put screening of these ligands in rhodium-, rutheni- cymene)]2, resulted in a mixture of diastereomeric
um- and iridium-mediated hydrogenations of a varie- complexes.
ty of alkenes and ketones revealed that these ligands
can deliver high enantioselectivity for alkenes (up to
98% ee) but are less selective when ketones are used Keywords: ferrocene ligands; hydrogenation; iridi-
as the substrates. The coordination behaviour of one um; phosphane ligands; rhodium; ruthenium
Introduction
the TRAP[6] and SPANphos[7] ligand families, Trostꢂs
phosphinoamides[8–10] (Figure 1) or phosphino-substi-
The transition metal-mediated enantioselective hydro- tuted cyclodextrins[5,11] have been investigated and
genation of alkenes, ketones and imines is considered have to some extent been successfully used as ligands
to be a very powerful and mature tool for the synthe- for asymmetric catalysts. Of all trans-spanning chiral
sis of chiral products and, as a consequence, this
methodology has found widespread applications in
both academia and industry.[1] In such transformations
rhodium, ruthenium or iridium complexes of chiral
phosphine ligands are mainly used as the catalyst pre-
cursors. Extensive efforts have been devoted to the
development of chiral phosphine ligands and thou-
sands of mainly cis-coordinating diphosphines have
been investigated.[1d,2] Despite this fact, the number of
broadly applicable or industrially suitable ligands still
remains small and hence ligand design continues to
be a central activity in catalyst development.
Interestingly, while most recent ligand development
has focused either on monophosphines[3] or cis-chelat-
ing diphosphines,[4] comparably little attention has
been devoted to the potential of trans-chelating di-
phosphine ligands. Indeed, in a very recent review
such trans-chelating ligands were fittingly referred to
Figure 1. trans-Spanning ligands TRAP, SPANphos and
Trostꢂs phosphino amides (bottom, left) and cis-coordinating
as ꢁelusive ligandsꢂ.[5] Nevertheless, a small number of
potentially trans-chelating chiral diphosphines such as Walphos ligands.
Adv. Synth. Catal. 2010, 352, 1063 – 1074
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Raffael Schuecker et al.
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ligands known to date, the TRAP ligand family shows these ligands in the rhodium-, ruthenium- and iridi-
by far the broadest range of applicability. The use of um-mediated enantioselective hydrogenation of al-
TRAP ligands leads to high conversion as well as kenes and ketones.
moderate to high product enantiomeric excess, not
only in the hydrogenation of alkenes and heterocy-
cles[12,13] but also in hydrosilylations,[14] Michael reac- Results and Discussion
tions,[15] aldol reactions[16] and other transforma-
tions.[17]
Ligand Synthesis and Coordination Behaviour
Over the years, our own efforts in ligand design
have resulted in the development of a number of cis- Starting from Ugiꢂs amine,[19] (R)-2, four derivatives
coordinating diphosphine ligand families including with varying phosphino substituents R were prepared
the so-called Walphos ligands (Figure 1).[18] While in a four-step sequence (Scheme 1).
TRAP ligands are biferrocene derivatives of molecu-
A Negishi coupling reaction[20] between (R)-N,N-di-
lar C2 symmetry, all Walphos ligands are based on a methyl-1-ferrocenylethylamine, (R)-2, and 2-diphenyl-
phenylferrocenylethyl backbone and this gives rise to phosphinylmethyl-iodobenzene, 3, gave the enantio-
molecular C1 symmetry. Furthermore, formation of merically pure key intermediate (R,Rp)-4. Iodoben-
square planar transition metal complexes (e.g., of Pd zene derivative 3 was easily obtained by reaction of 2-
or Pt) of Walphos-type ligands results in cis-coordina- iodobenzyl bromide and diphenylphosphine oxide in
tion and in the formation of eight-membered chelate toluene/aqueous KOH under phase transfer condi-
rings.[18a] In contrast, TRAP ligands give nine-mem- tions.[21] Treatment of (R,Rp)-4 with either a diaryl- or
bered chelate rings[6] with mainly trans-coordinated li- dialkylphosphine R2PH in acetic acid[22] led to deriva-
gands. In this context we considered that extending tives (R,Rp)-5a–5d [R=Ph: 5a; 3,5-Me2-4-OMe-C6H2:
the Walphos backbone by one carbon would also lead 5b; Cy: 5c; t-Bu: 5d], which were isolated in the form
to trans-coordinating ligands.
of their borane complexes (R,Rp)-5aACHTUGNTRENNU(G BH3)–5dACHTUNGTRENNUNG(BH3)
In this contribution we report the synthesis of four in order to facilitate purification and/or characterisa-
[23]
representatives of a new family of diphosphine li- tion. Subsequent reduction with LiAlH4/AlCl3 gave
gands, all of which have a methylphenyl-ferroceny- products 1a–1d, which were also isolated as borane
lethyl backbone. In addition, we describe NMR re- complexes (R,Rp)-1a
N
ACHTUGNTRENUN(GN BH3)2. Finally, borane
sults that shed light on the coordination behaviour of decomplexation was accomplished by treatment with
these ligands and provide a summary of the results either diethylamine [1aACHTGNUTRENNUNG
obtained in an extensive high throughput screening of
Scheme 1. Synthesis of ligands 1a–1d.
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Ferrocenyl-Aryl Based trans-Chelating Diphosphine Ligands
Figure 2. Molecular structures of 5cCAHTUNGTREN(GNUN BH3) (left), 1aAHCUTNRTEGN(GUNN BH3)2 (middle) and 1cACHTNUGTRNE(NUGN BH3)2 (right) in the crystalline state; ring-bonded
H-atoms omitted for clarity.
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
X-ray diffraction (Figure 2).
In order to assess its coordination behaviour, ligand All ligands of (R,Rp) configuration (1a–1d) were
1a was reacted with [PdCl2ACHTNUTRGNEUNG(MeCN)2] in different sol- screened in catalytic hydrogenations of a number of
vents and the resulting products were analysed by alkenes and ketones using a customised Symyx high
1
NMR spectroscopy. The H and 31P{1H} NMR spectra throughput screening system (for substrates see
showed that in apolar solvents like benzene signifi- Figure 3). All catalysts were formed in situ by reacting
cant amounts of oligomeric species of undefined the ligands with an appropriate Rh, Ru or Ir source
nature were formed, while in chloroform and dime- and, depending on the substrate, standard test reac-
thylformamide only one complex was obtained – tion conditions were used. The best results obtained
along with small amounts of oligomers. The 31P NMR in alkene hydrogenations are listed in Table 1 and
spectrum (CDCl3) of 1a showed one AB system [d typical results for ketone hydrogenations are summar-
(ppm) PA: 20.2, PB: 25.3] with a coupling constant of ised in Table 2 (for reaction conditions see footnotes
2JP, P =568 Hz and this clearly indicates trans-coordina- to Table 1 and Table 2). In combination with [Rh-
tion of the diphosphine ligand.[25,26] Furthermore,
ligand 1a was reacted with trans-[PtCl2A(MeCN)2] in particular proved to be a very valuable ligand in the
dichloromethane.[6d] Once again only one trans-coor- asymmetric hydrogenation of alkenes (Table 1).
ACHTUNGTRENNUG(NBD)2]BF4 or [RuCl2ACHUTNGTRENN(NGU p-cymene)]2 diphosphine 1c in
CTHUNGTRENNUNG
dinated complex was detected and this was accompa-
The use of ligand 1c led to high to excellent prod-
nied by some oligomeric species. In the 31P NMR uct enantiomeric excess as well as quantitative or
2
spectrum both the JP, P coupling constant of the ob- close to quantitative conversion in the hydrogenation
2
served AB system [d (ppm) PA: 14.7, PB: 19.9; JP. P
=
of substrates methyl acetamidoacrylate (MAA), ethyl
503 Hz] and the J
coupling constants, which can Z-b-acetamidocrotonate (Z-EAAC), Z-a-acetamido-
195Pt,P
be extracted from the platinum satellites, are indica- cinnamic acid (ACA) and dimethyl itaconate (DMI).
tive of a trans-coordinated ligand [J195Pt,P(A) =2650 Hz; Particularly outstanding results were obtained with
J
195Pt,P(B) =2684 Hz] as part of a square planar com- the enamides MAA, Z-EAAC and ACA, which gave
plex.[5,6d] Reaction of ligand 1a in methanol with products with 94–97% ee at conversions of 98% or
[RuCl2A(p-cymene)]2 in the presence of one equivalent better (Table 1, entries 1, 4, 10 and 13). For substrates
CHTUNGTRENNUNG
of AgNO3 followed by the addition of NH4PF6 led to 1-acetamido-3,4-dihydronaphthalene (DHNAA), E-2-
the formation of two diastereomeric complexes methyl-3-phenyl-prop-2-enol (AllylOH), methyl Z-a-
[RuClACHTUNGTRENNUNG
(cymene)(1a)]PF6 in a 7:5 ratio. The 31P NMR acetamidocinnamate (MAC) and E-2-methylcinnamic
spectrum of this mixture of diastereomers shows two acid (MCA) the product enantioselectivities were in
doublets for each stereomer [d (ppm) major diaste- the range 74–89% [DHNAA (conv./ee): 99/89; Ally-
2
reomer: PA: 16.0, PB: 20.2; JP, P =48.7 Hz; minor dia- lOH: >99/82; MAC: >99/75; MCA: >99/74; Table 1,
2
stereomer: PA: 11.3, PB: 25.8; JP, P =47.0 Hz] with cou- entries 18, 21, 23 and 24]. In the hydrogenation of Al-
pling constants that are typical of chelating ligands in lylOH, MAC and MCA ligand 1c again proved to be
piano stool-type ruthenium arene complexes.[27] Based superior, although in the case of DHNAA the best re-
on these experiments we expected diphosphines 1a– sults were obtained with ligand 1b. As one might
1d to be well able to coordinate to appropriate metals expect, the product enantiomeric excess is highly de-
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Figure 3. Alkenes and ketones used as substrates in catalytic hydrogenations.
Table 1. Best results obtained in alkene hydrogenations with ligands 1a–1d.[a]
Entry
Substrate
Metal Precursor
[RuCl2A(p-cymene)]2
Lig.
S/C
Additive[b]
Solvent[c]
Conv.
% ee
1
2
3
4
5
6
7
8
MAA
MAA
G
E
1c
1c
1c
1c
1c
1c
1a
1a
1c
1c
1c
1c
1c
1c
1c
1b
1b
1b
1b
1b
1c
1c
1c
1c
1c
1c
1c
1c
25
25
25
100
25
100
100
100
25
25
100
25
100
25
100
25
25
100
25
100
100
100
25
25
25
EtOH
EtOH
EtOH
EtOH
THF
THF
EtOH
THF
EtOH
EtOH
EtOH
EtOH
EtOH
THF
98
62
>99
>99
>99
84
95
98
96
97
95
96
72
70
92
94
90
88
91
88
90
72
85
89
73
74
82
74
75
74
73
70
48
48
A
U
DABCO
TFA
TFA
TFA
TFA
Z-EAAC
Z-EAAC
Z-EAAC
Z-EAAC
Z-EAAC
Z-EAAC
ACA
ACA
ACA
DMI
DMI
DMI
DMI
DMI
DHNAA
DHNAA
DHNAA
DHNAA
AllylOH
AllylOH
MAC
E
R
R
N
R
R
TFA
TFA
99
77
9
A
U
>99
>99
89
>99
>99
>99
>99
>99
>99
99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
A
U
DABCO
DABCO
A
U
E
E
ACHTUNGTRENNUNG
T
THF
E
EtOH
MeOH
MeOH
TFA
TFA
DCE
A
U
A
U
R
R
R
E
TFA
THF
R
MCA
MCA
MCA
E-EAAC
E-EAAC
A
U
MeOH
MeOH
MeOH
EtOH
EtOH
A
U
A
U
100
25
100
ACHTUNGTRENNUNG
G
[a]
Reaction conditions: 2 mmol of ligand; 0.83 equivalents of metal precursor; MAA, Z-EAAC, ACA, DMI: p(H2) 1 bar, T
258C, reaction time 2 h; DHNAA: p(H2) 5 bar, T 258C, 16 h; AllylOH: p(H2) 20 bar, T 258C, 16 h; MCA p(H2) 20 bar, T
258C, reaction time 2 h.
[b]
[c]
DABCO: 1,4-diazabicyclo
ACHTUNGTRENNUNG
DCE: dichloroethane.
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Ferrocenyl-Aryl Based trans-Chelating Diphosphine Ligands
Table 2. Typical results in ketone hydrogenations with ligands 1a–1d.[a]
Entry
Substrate
Metal Precursor
[Ir(COD)Cl]2
Lig.
S/C
Additive
Solvent
Conv.
% ee
1
2
3
4
5
6
7
8
9
10
MPG
MPG
MPG
Etpy
KPL
N
1b
1a
1a
1c
1c
1a
1c
1b
1a
11
25
25
25
25
25
25
100
100
100
100
DABCO
DABCO
DABCO
DABCO
DCE, THF
THF, toluene
THF, toluene
EtOH, THF
toluene
EtOH, THF
EtOH
EtOH
56
97
97
99
42
>99
17
33
89
68
41
41
60
70
52
55
38
41
43
[Rh
[Rh
[Rh
[Rh
[Rh
N
E
KPL
DABCO
AcCl (HCl)
AcCl (HCl)
EOP
EOP
EBA
ETAA
A
U
A
U
R
EtOH
EtOH
.
A
HBF4 Et2O
>99
[a]
Reaction conditions: 2 mmol of ligand; 0.83 equivalents of metal precursor; MPG, Etpy, KPL: p(H2) 20 bar, T 258C, reac-
tion time 14 h; EOP, EBA, ETAA: p(H2) 80 bar, T 808C, reaction time 14 h.
pendent on the substrate configuration. In the case of [RuCl
the Z-EAAC product an ee of 97% was obtained, but reomeric half sandwich-type complexes. It is conclud-
with E-EAAC only 48% ee was reached. ed that ligands 1a–1d are able to coordinate to appro-
2ACHTUNGTERN(NUNG p-cymene)]2 resulted in a mixture of diaste-
In almost all alkene hydrogenations (Table 1) either priate metals in a trans-fashion but they can also
alcohols (methanol and ethanol) or THF proved to be easily adopt much narrower bite angles. All four li-
the solvent of choice. Interestingly, on changing the gands were tested by high throughput screening in the
solvent from alcohol to THF the product enantiomer- hydrogenation of nine alkenes and six ketones. It was
ic excess remained almost unaffected (Table 1, en- found that these ligands deliver high enantioselectivi-
tries 3/5, 4/6, 7/8, 12/14 and 13/15) but in some cases ty with alkene substrates but are not as effective with
such a change resulted in significantly lower conver- ketones. In particular, the catalysts prepared in situ
sion (Table 1, entries 4/6 and 7/8). When substrates from ligand 1c in combination with [Rh
ACHTUNGTERN(NUNG NBD)2]BF4
MAA and ACA were used the addition of base or [RuCl2A(p-cymene)]2 in the hydrogenation of the en-
CTHUNGTRENNUNG
(DABCO) led to a slight increase in ee values amides methyl acetamidoacrylate, ethyl Z-b-acetami-
(Table 1, entries 1/2 and 9/10) but with MAA as the docrotonate, Z-a-acetamidocinnamic acid (all precur-
substrate the conversion dropped from 98 to 62% (en- sors of a- or b-amino acid derivatives) and dimethyl
tries 1/2).
itaconate gave products with 94–97% ee at conver-
In the hydrogenation of ketones (Table 2 and sions of 98% or better.
Figure 3) the catalysts prepared in situ from ligands
1a–1d and an appropriate Rh, Ru or Ir source did not
perform nearly as well as in the alkene hydrogena-
tions. Indeed, a product with both a high conversion
Experimental Section
and high enantioselectivity was not obtained in any
case.
General Considerations
NMR spectra were recorded on a Bruker DPX-400 spec-
trometer in CDCl3. Chemical shifts (d) are given relative to
CHCl3 (1H: 7.26 ppm), CDCl3 (13C: 77.0 ppm) and 85%
H3PO4 (31P: 0 ppm). The coupling constants in 13C{1H} spec-
tra are due to 13C-31P coupling. For signal assignment the
following terms were used: s, bs, d, bd, dd, t and m refer to
singlet, broad singlet, doublet, broad doublet, doublet of
Conclusions
In summary, a selection of four chiral and potentially
trans-coordinating diphosphines 1a–1d, all based on a
methylphenyl-ferrocenylethyl backbone, is described. doublets, triplet and multiplet, respectively. The terms PhA–D
were used for phenyl or aryl groups of diphenylphosphino
or diarylphosphino units. In this respect, superscripts A–D
were used to distinguish between rings attached to different
phosphorus atoms. A general atom numbering Scheme used
for proton and carbon assignment is given in Figure 4. Melt-
ing points were determined on a Kofler melting point appa-
ratus and are uncorrected. Mass spectra were recorded on
Finnigan MAT 900 and MAT 95 spectrometers. Optical ro-
tations were measured on a Perkin–Elmer 241 polarimeter.
All reactions required inert conditions and were carried out
All ligands were synthesised in a four-step sequence
from enantiopure N,N-dimethylaminoethylferrocene
(Ugiꢂs amine) and the molecular structures in the
solid state of three representatives, together with their
absolute configuration, were determined by X-ray dif-
fraction. The coordination behaviour of one ligand
(1a) in its square planar palladium and platinum di-
chloride complexes was studied by 31P NMR and only
trans-chelated complexes – together with oligomeric
by-products – were observed. Reaction of 1a with under an argon atmosphere using standard Schlenk tech-
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and the remaining mass was suspended in a mixture of di-
ethyl ether (500 mL), dichloromethane (50 mL) and an
aqueous solution of sodium hydroxide (5M, 200 mL). After
vigorous shaking and phase separation, the aqueous phase
was extracted with diethyl ether (2ꢄ100 mL). The combined
organic phases were washed with water and brine. After
drying over MgSO4 and removal of the solvents under re-
duced pressure, the crude product was purified by chroma-
tography on aluminum oxide 90 (eluent EA/TEA=9/1). A
second purification step involved dissolution of the chroma-
tographed product in a minimum amount of DCM and addi-
tion of hexanes until precipitation occurred. The orange
solid was filtered off, washed with hexanes and dried under
vacuum; yield: 9.88 g (18.05 mmol, 64%); [a]2l0 (nm): +66.3
(589), +55.6 (578), À29.3 (546) (c 1.141, CHCl3); mp 1818C;
1H NMR (400 MHz, CDCl3): d=1.52 (d, J=6.9 Hz, 3H,
Figure 4. Atom numbering Scheme for NMR structure as-
signment for 3 (left) and backbone of ferrocenes 1, 4, 5
(right).
niques. All solvents were dried by standard procedures and
distilled before use. Chromatographic separations were per-
formed under gravity on standardised aluminium oxide 90
(Merck). Petroleum ether with a boiling range of 55–658C
was used for chromatography. Abbreviations: PE: petrole-
um ether, DEE: diethyl ether; EA: ethyl acetate; TEA: tri-
CHCH3), 1.70 [s, 6H, N
1H, CHAHB), 3.46 (q, J=6.9 Hz, 1H, CHCH3), 3.78 (dd,
H,H =14.6 Hz, JH,P =13.6 Hz, 1H, CHAHB), 4.11 (s, 5H,
ACTHGNUTERN(NUNG CH3)2], 3.35 (t, JH,H =JH,P =14.6 Hz,
ACHTUNGTRENNUNGethylamine; DCM: dichloromethane.
J
Cp’), 4.18–4.22 (m, 2H, H2+H4), 4.22–4.25 (m, 1H, H3),
7.04–7.12 (m, 2H, H9+H10), 7.20–7.28 (m, 1H, H8), 7.35–
7.43 (m, 2H, PhB-meta), 7.45–7.60 (m, 6H, PhA-meta+PhB-
ortho+PhA-para+PhB-para), 7.67–7.77 (m, 2H, PhA-ortho),
7.85 (d, J=7.7 Hz, 1H, H7); 13C NMR (100.6 MHz, CDCl3):
d=18.3 (s, CHCH3), 34.8 (d, J=67.7 Hz, CH2), 40.8 [s, N-
Ligand Synthesis
2-Diphenylphosphinylmethyl-iodobenzene (3): To a solution
of 2-iodobenzyl bromide (10.00 g, 33.68 mmol) in toluene
(100 mL) were added diphenylphosphine oxide (6.81 g,
33.68 mmol),
tetrabutylammonium
bromide
(1.09 g,
AHCTNUGTER(GNNNU CH3)2], 54.9 (s, CHCH3), 66.2 (s, C3), 66.4 (s, C4), 69.5 (s,
3.368 mmol) and aqueous potassium hydroxide solution
(30%, 100 mL). The resulting biphasic mixture was stirred
at 1008C for 3 h. After cooling, the phases were separated
and the aqueous phase was extracted with diethyl ether (3ꢄ
50 mL). The combined organic phases were washed with
water and brine, dried over MgSO4 and the solvents were
removed under reduced pressure. Recrystallisation of the
crude product from PE/benzene=1/1 afforded the title com-
pound as a colourless solid; yield: 6.98 g (16.69 mmol,
C2), 69.9 (s, Cp’), 89.1 (s, C1+C5), 125.9 (d, J=2.5 Hz, C8),
126.5 (d, J=2.3 Hz, C9), 128.4 (d, J=3.9 Hz, PhA/B-meta),
128.5 (d, J=3.8 Hz, PhA/B-meta), 129.5 (d, J=4.4 Hz, C10),
131.0 (d, J=9.2 Hz, PhB-ortho), 131.4 (d, J=7.6 Hz, C11),
131.6 (d, J=3.1 Hz, PhA-para), 131.7–131.9 (m, PhA-ortho+
PhB-para), 131.9 (d, J=98.4 Hz, PhA-ipso), 133.8 (d, J=
1.3 Hz, C7), 134.0 (d, J=98.1 Hz, PhB-ipso), 137.7 (d, J=
6.7 Hz, C6); 31P NMR (162 MHz, CDCl3): d=31.0 (s); HR-
MS (ESI): m/z=548.1809, calcd. for C33H35FeNOP [M +
H]+: 548.1806.
1
50%); mp 1008C; H NMR (400 MHz, CDCl3): d=3.91 (d,
J=13.9 Hz, 2H, CH2), 6.83–6.91 (m, 1H, H3), 7.21–7.29 (m,
1H, H4), 7.40–7.64 (m, 4H, Ph-meta), 7.49–7.55 (m, 2H, Ph-
para), 7.57–7.62 (m, 1H, H5), 7.66–7.74 (m, 5H, Ph-ortho+
H2); 13C NMR (100.6 MHz, CDCl3): d=42.3 (d, J=65.9 Hz,
C7), 102.3 (d, J=7.8 Hz, C1), 128.3 (d, J=2.6 Hz, C4), 128.5
(d, J=11.7 Hz, Ph-meta), 128.6 (d, J=2.6 Hz, C3), 131.0 (d,
J=4.5 Hz, C5), 131.3 (d, J=9.4 Hz, Ph-ortho), 131.9 (d, J=
2.5 Hz, Ph-para), 132.0 (d, J=99.6 Hz, Ph-ipso), 135.1 (d,
J=7.3 Hz, C6), 139.5 (d, J=8.1 Hz, C2); 31P NMR
(162 MHz, CDCl3): d=30.7 (s); HR-MS (ESI): m/z=
419.0078, calcd. for C19H17IOP [M+H]+: 419.0062.
General Procedure for the Synthesis of (R,Rp)-
5a
ACHTUTGNRNE(NUG BH3)–(R,Rp)-5dACHTUGNTREN(NUGN BH3)
A
degassed solution of (R,Rp)-4 (2.00 g, 3.65 mmol,
1.0 equiv.) and the appropriate dialkyl- or diarylphosphine
(for the exact amounts see below) in acetic acid (10 mL)
was stirred for 16 h at 1008C. After cooling, the solvent was
removed under reduced pressure and the remaining semisol-
id mass was treated with a solution of borane in THF
(1.0M, 10.00 mmol). Stirring was continued for 2 h at room
temperature followed by quenching with water. The mixture
was extracted with EA (2ꢄ150 mL) and the combined or-
ganic phases were washed with water and brine and dried
over MgSO4. After removal of the solvents under reduced
pressure the pure products were obtained after either re-
crystallisation or column chromatography.
ACHTUNGTRENNUNG(R,Rp)-2-[1-(N,N-Dimethylaminoethyl)]-1-[2-(diphenyl-
phosphinylmethyl)-phenyl]ferrocene [(R,Rp)-4]: To a stirred
solution of (R)-2 (9.00 g, 35.00 mmol) in THF (30 mL)
cooled to 08C was added dropwise a solution of s-BuLi in
cyclohexane (1.4M, 27.5 mL, 38.50 mmol). The resulting
mixture was stirred for 3 h at 08C. A solution of zinc bro-
mide in THF (1.3M, 32.3 mL, 42.00 mmol) was added and
the mixture was stirred for a further 30 min at 08C and for
AHCTUNGTRENNUNG
1 h at room temperature. In
a separate flask, [Pd2
A
ACHTUNGTRENNUNG
(1.63 g, 7.00 mmol) were suspended in THF (45 mL) and
stirred at room temperature for 15 min. To this solution was
added 3 (11.71 g, 28.00 mmol) dissolved in THF (60 mL) fol-
lowed by the organozinc species. The resulting mixture was
stirred for 16 h at 758C. After cooling to room temperature,
the solvent was reduced to one third of its initial volume
phosphine were used and the product was crystallised from
EA as yellow crystals; yield: 2.18 g (3.10 mmol, 85%); [a]l20
(nm): +110.9 (589), +104.1 (578), +40.6 (546) (c 1.024,
CHCl3); mp 878C; 1H NMR (400 MHz, CDCl3): d=0.23–
1.43 (bd, 3H, BH3), 1.72 (dd, J=16.2 Hz, J=7.3 Hz, 3H,
CHCH3), 2.42 (t, JH,H =JH,P =14.9 Hz, 1H, CHAHB), 3.04
1068
asc.wiley-vch.de
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 1063 – 1074

Ferrocenyl-Aryl Based trans-Chelating Diphosphine Ligands
(dd, JH,H =14.9 Hz, JH,P =11.9 Hz, 1H, CHAHB), 3.64–3.76
(m, 1H, CHCH3), 4.05 (s, 5H, Cp’), 4.13–4.15 (m, 1H, H2),
4.22–4.24 (m, 1H, H3), 4.50–4.52 (m, 1H, H4), 6.90 (d, J=
7.8 Hz, 1H, H10), 6.93–7.04 (m, 4H, PhC-ortho+PhC-meta),
7.08–7.16 (m, 2H, PhC-para+H9), 7.30–7.46 (m, 8H, PhB-
ortho+PhB-meta+PhB-para+PhD-meta+H8), 7.47–7.57 (m,
5H, PhD-ortho+PhA-meta+PhA-para), 7.58–7.64 (m, 1H,
PhD-para), 7.65–7.73 (m, 2H, PhA-ortho), 7.86 (d, J=7.8 Hz,
1H, H7); 13C NMR (100.6 MHz, CDCl3): d=19.4 (d, J=
5.4 Hz, CHCH3), 27.0 (d, J=31.0 Hz, CHCH3), 34.1 (d, J=
67.2 Hz, CHAHB), 66.8 (s, C3), 68.1 (s, C4), 68.7 (s, C2), 70.2
(s, Cp’), 87.4 (s, C1), 89.4 (d, J=5.3 Hz, C5), 125.9 (d, J=
2.5 Hz, C8), 126.5 (d, J=2.2 Hz, C9), 128.0 (d, J=9.8 Hz,
PhC-meta), 128.4, 128.49, 128.57, 128.61, 128.66 (PhA-meta+
PhB-meta+PhD-meta), 128.3, 128.9, 129.0 (2 Ph-ipso) 130.3
(d, J=2.1 Hz, C10), 130.4 (d, J=3.8 Hz, PhC-para), 130.9 (d,
J=9.2 Hz, PhB-ortho), 131.0 (d, J=3.0 Hz, PhB-para), 131.6
(d, J=7.9 Hz, C11), 131.6 (d, J=98.3 Hz, PhA-ipso), 131.7
(d, J=2.5 Hz, PhD-para), 131.8 (d, J=8.9 Hz, PhA-ortho),
131.9 (d, J=2.5 Hz, PhA-para), 132.6 (d, J=7.8 Hz, PhC-
ortho), 132.7 (d, J=8.2 Hz, PhD-ortho), 133.4 (d, J=1.4 Hz,
C7), 134.0 (d, J=98.3 Hz, Ph-ipso), 136.8 (d, J=6.0 Hz, C6);
31P NMR (162 MHz, CDCl3): d=27.3 (bs, C13-P), 31.1 (s,
C12-P); PhA and PhB connected to C12-P, PhC and PhD con-
nected to C13-P; HR-MS (ESI): m/z=702.2088, calcd. for
C43H41BFeOP2 [M]+: 702.2084.
J=98.1 Hz, PhB-ipso), 136.9 (d, J=5.9 Hz, C6), 158.7 (d, J=
2.8 Hz, PhC-para), 159.3 (d, J=2.9 Hz, PhD-para); 31P NMR
(162 MHz, CDCl3): d=24.5 (bs, C13-P), 30.4 (s, C12-P); PhA
and PhB connected to C12-P, PhC and PhD connected to
C13-P; HR-MS (ESI): m/z=818.2927, calcd. for
C49H53BFeO3P2 [M]+: 818.2922.
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
ylphosphine were used and the crude product was crystal-
lised from EA to give red crystals. Crystals suitable for X-
ray diffraction were grown by slow diffusion of hexane into
a concentrated solution of the compound in CDCl3; yield:
1.98 g (2.77 mmol, 76%); [a]2l0 (nm): +82.2 (589), +73.8
(578), +5.3 (546) (c 1.081, CHCl3); mp 2198C (dec.);
1H NMR (400 MHz, CDCl3): d=À0.39–0.55 (bd, 3H, BH3),
0.65–1.76 (m, 22H, Cy), 1.78 (dd, J=14.1 Hz, J=7.5 Hz,
3H, CHCH3), 2.97–3.08 (m, 1H, CHCH3), 3.41 (t, JH,H
J
=
H,P =14.6 Hz, 1H, CHAHB), 4.03–4.13 (m, 1H, CHAHB),
4.07 (s, 5H, Cp’), 4.26–4.29 (m, 1H, H3), 4.30–4.34 (m, 1H,
H4), 4.44–4.47 (m, 1H, H2), 7.03–7.12 (m, 2H, H9+H10),
7.24–7.30 (m, 1H, H8), 7.38–7.44 (m, 2H, PhB-meta), 7.48–
7.58 (m, 5H, PhA-meta+PhB-ortho+PhB-para), 7.59–7.65
(m, 1H, PhA-para), 7.77–7.85 (m, 2H, PhA-ortho), 7.88 (d,
J=7.8 Hz, 1H, H7); 13C NMR (100.6 MHz, CHCl3): d=19.8
(d, J=2.3 Hz, CHCH3), 22.6 (d, J=25.3 Hz, CHCH3), 25.8
(s, Cy), 26.6–27.3 (m, Cy), 30.8 (d, J=18.2 Hz, Cy), 31.1 (d,
J=18.5 Hz, Cy), 35.6 (d, J=66.9 Hz, CHAHB), 66.6 (s, C3),
67.7 (s, C4), 69.3 (s, C2), 70.3 (s, Cp’), 87.4 (s, C1), 92.0 (s,
C5), 126.3 (d, J=2.4 Hz, C8), 126.8 (d, J=2.4 Hz, C9), 128.5
(d, J=8.2 Hz, PhA/B-meta), 128.7 (d, J=8.1 Hz, PhA/B-meta),
130.5 (d, J=3.9 Hz, C10), 130.9 (d, J=9.3 Hz, C11), 131.0
(d, J=9.2 Hz, PhB-ortho), 131.4 (d, J=96.9 Hz, PhA-ipso),
131.8 (d, J=2.7 Hz, PhB-para), 131.9 (d, J=8.8 Hz, PhA-
ortho), 132.0 (d, J=2.7 Hz, PhA-para), 133.9 (d, J=2.3 Hz,
C7), 134.0 (d, J=98.0 Hz, PhB-ipso), 137.3 (d, J=5.8 Hz,
C6); 31P NMR (162 MHz, CHCl3): d=31.1 (s, C12-P), 38.7
(bs, C13-P); PhA and PhB connected to C12-P; HR-MS
(ESI): m/z=714.3031, calcd. for C43H53BFeOP2 [M]+:
714.3023.
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
2.0 equiv. of bis(3,5-dimethyl-4-methoxyphenyl)phosphine
were used and the crude product was purified by column
chromatography on aluminum oxide 90 with DCM/EA=5/1
as the eluent to give the title compound as a yellow foam;
yield: 2.52 g (3.08 mmol, 84%); [a]2l0 (nm): +129.0 (589),
+122.4 (578), +58.3 (546) (c 1.051, CHCl3); mp 1208C;
1H NMR (400 MHz, CDCl3): d=0.29–1.26 (bs, 3H, BH3),
1.69 (dd, J=16.3 Hz, J=7.3 Hz, 3H, CHCH3), 1.91 (s, 6H,
PhC-CH3), 2.22 (s, 6H, PhD-CH3), 2.43 (t, JH,H =JH,P
14.3 Hz, 1H, CHAHB), 2.98 (dd,
H,H =14.3 Hz, JHP
=
=
J
13.1 Hz, 1H, CHAHB), 3.54 (s, 3H, PhC-OCH3), 3.58–3.70
(m, 1H, CHCH3), 3.70 (s, 3H, PhD-OCH3), 4.08 (s, 5H, Cp’),
4.23–4.27 (m, 1H, H3), 4.42–4.45 (m, 1H, H2), 4.49–4.52 (m,
1H, H4), 6.58 (d, J=10.3 Hz, 2H, PhC-ortho), 6.66 (d, J=
7.8 Hz, 1H, H10), 7.03 (t, J=7.2 Hz, 1H, H9), 7.13 (d, J=
9.8 Hz, 2H, PhD-ortho), 7.28–7.34 (m, 1H, H8), 7.38–7.44
(m, 2H, PhB-meta), 7.45–7.55 (m, 5H, PhA-meta+PhB-
ortho+PhB-para), 7.56–7.61 (m, 1H, PhA-para), 7.67–7.74
(m, 2H, PhA-ortho), 7.87 (d, J=7.6 Hz, H7); 13C NMR
(100.6 MHz, CDCl3): d=16.0 (s, PhC-CH3), 16.3 (s, PhD-
CH3), 19.1 (d, J=5.7 Hz, CHCH3), 27.5 (d, J=31.4 Hz,
CHCH3), 33.8 (d, J=67.2 Hz, CHAHB), 59.3 (s, PhC-OCH3),
59.5 (s, PhD-OCH3), 66.6 (s, C3), 68.1 (s, C4), 68.9 (s, C2),
70.1 (s, Cp’), 87.3 (s, C1), 89.5 (d, J=5.0 Hz, C5), 122.6,
122.98, 123.19, 123.51 (PhC-ipso+PhD-ipso), 125.6 (d, J=
2.5 Hz, C8), 126.2 (d, J=2.4 Hz, C9), 128.5 (d, J=11.6 Hz,
PhA/B-meta), 128.5 (d, J=11.6 Hz, PhA/B-meta), 129.7 (d, J=
3.9 Hz, C10), 130.3 (d, J=10.9 Hz, PhC-meta), 130.9 (d, J=
9.2 Hz, PhB-ortho), 131.3 (d, J=10.4 Hz, PhD-meta), 131.5
(d, J=4.3 Hz, C11), 131.6 (d, J=2.8 Hz, PhA-para), 131.7 (d,
J=8.1 Hz, PhA-ortho), 131.8 (s, PhB-para), 131.9 (d, J=
111.3 Hz, PhA-ipso), 133.2 (d, J=9.2 Hz, PhD-ortho), 133.3
(d, J=1.7 Hz, C7), 133.6 (d, J=9.3 Hz, PhC-ortho), 134.2 (d,
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
phosphine were used and the crude product was crystallised
from EA to give red crystals; yield: 1.72 g (2.59 mmol,
71%); [a]2l0 (nm): +98.8 (589), +89.4 (578), +11.5 (546) (c
1.184, CHCl3); mp 2278C (dec.); 1H NMR (400 MHz,
CDCl3): d=À0.71–0.42 (bd, 3H, BH3), 0.84 [d, J=12.1 Hz,
9H, CA(CH3)3], 1.28 [d, J=12.1 Hz, 9H, CB
ACHTNUGTRENNUG AHCTUNGTREN(NUGN CH3)3], 2.08
(dd, J=10.4 Hz, J=7.6 Hz, 3H, CHCH3), 3.04–3.15 (m, 1H,
CHCH3), 3.51 (dd, H,H =15.1 Hz, H,P =12.9 Hz, 1H,
CHAHB), 4.09 (s, 5H, Cp’), 4.23 (dd, JH,H =15.1 Hz, JH,P
J
J
=
13.3 Hz, 1H, CHAHB), 4.26–4.29 (m, 2H, H2+H4), 4.56–
4.59 (m, 1H, H3), 6.92–6.96 (m, 1H, H10), 6.97–7.03 (m,
1H, H9), 7.19–7.25 (m, 1H, H8), 7.37–7.43 (m, 2H, PhB-
meta), 7.46–7.53 (m, 3H, PhA-meta+PhB-para), 7.54–7.61
(m, 3H, PhB-ortho+PhA-para), 7.77–7.86 (m, 3H, H7+PhA-
ortho); 13C NMR (100.6 MHz, CDCl3): d=22.6 (d, J=
2.9 Hz, CHCH3), 25.9 (d, J=21.0 Hz, CHCH3), 28.1 [s, CB-
A
R
ACHTUNGTRENNUNG(CH3)3],
AHCTUNGTRENNUNG
Adv. Synth. Catal. 2010, 352, 1063 – 1074
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1069

Raffael Schuecker et al.
FULL PAPERS
88.7 (s, C1), 93.7 (d, J=5.2 Hz, C5), 125.7 (d, J=2.8 Hz,
31P NMR (162 MHz, CDCl3): d=19.1 (bs, C12-P), 27.5 (bs,
C13-P); PhA and PhB connected to C12-P, PhC and PhD con-
nected to C13-P; HR-MS (ESI): m/z=700.2458, calcd. for
C43H44B2FeP2 [M]+: 700.2469.
C8), 126.4 (d, J=2.4 Hz, C9), 128.4 (d, J=5.8 Hz, PhA/B
-
meta), 128.5 (d, J=5.6 Hz, PhA/B-meta), 130.5 (d, J=4.2 Hz,
C10), 131.0 (d, J=9.2 Hz, PhB-ortho), 131.5 (d, J=2.2 Hz,
PhA-para), 131.7 (d, J=2.2 Hz, PhB-para), 131.9 (d, J=
8.5 Hz, C11), 132.0 (d, J=9.2 Hz, PhA-ortho), 132.1 (d, J=
98.1 Hz, PhA-ipso), 133.5 (s, C7), 134.5 (d, J=97.6 Hz, PhB-
ipso), 137.8 (d, J=6.0 Hz, C6); 31P NMR (162 MHz, CDCl3):
d=31.5 (s, C12-P), 57.6 (bs, C13-P); PhA and PhB connected
to C12-P; HR-MS (EI, 308C): m/z=662.2733, calcd. for
C39H49BFeOP2 [M]+: 662.2709.
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
was obtained after column chromatography on aluminum
oxide 90 (eluent: PE/DCM=2/5) as a yellow foam; yield:
2.08 g (2.55 mmol, 93%); [a]2l0 (nm): +132.8 (589), +125.9
(578), +58.8 (546) (c 1.076, CHCl3); mp 1048C; 1H NMR
(400 MHz, CDCl3): d=À0.24–1.44 (bs, 6H, C12-P-BH3
+
General Procedure for the Synthesis of (R,Rp)-
C13-P-BH3), 1.66 (dd, J=16.4 Hz, J=7.3 Hz, 3H, CHCH3),
1.97 (s, 6H, PhC-CH3), 2.23 (s, 6H, PhD-CH3), 2.47–2.50 (m,
1H, CHAHB), 3.03 (dd, JH,H =14.6 Hz, JH,P =9.7 Hz, 1H,
CHAHB), 3.58 (s, 3H, PhC-OCH3), 3.55–3.66 (m, 1H,
CHCH3), 3.69–3.72 (m, 1H, H2), 3.71 (s, 3H, PhD-OCH3),
3.99 (s, 5H, Cp’), 4.21 (t, J=2.5 Hz, 1H, H3), 4.47–4.51 (m,
1H, H4), 6.54 (d, J=10.3 Hz, 2H, PhC-ortho), 6.67–6.71 (m,
1H, H10), 7.04–7.10 (m, 1H, H9), 7.11 (d, J=9.8 Hz, 2H,
PhD-ortho), 7.31–7.42 (m, 5H, PhB-ortho+PhB-meta + H8),
7.43–7.52 (m, 3H, PhA-meta+PhB-para), 7.54–7.61 (m, 1H,
PhA-para), 7.61–7.68 (m, 2H, PhA-ortho), 7.83 (d, J=7.7 Hz,
1H, H7); 13C NMR (100.6 MHz, CDCl3): d=16.1 (s, PhC-
CH3), 16.3 (s, PhD-CH3), 18.9 (d, J=5.9 Hz, CHCH3), 27.5
(d, J=31.3 Hz, CHCH3), 30.1 (d, J=31.9 Hz, CHAHB), 59.4
(s, PhC-OCH3), 59.5 (s, PhD-OCH3), 66.5 (s, C3), 68.1 (d, J=
1.2 Hz, C4), 68.2 (s, C2), 70.1 (s, Cp’), 86.4 (s, C1), 89.8 (d,
J=4.7 Hz, C5), 122.5, 122.7, 123.0, 123.3 (PhC-ipso+PhD-
ipso), 125.8 (d, J=2.6 Hz, C8), 126.1 (d, J=2.2 Hz, C9),
127.8 (d, J=53.8 Hz, PhA-ipso), 128.6 (d, J=9.8 Hz, PhB-
meta), 128.7 (d, J=9.9 Hz, PhA-meta), 129.5 (d, J=3.8 Hz,
C10), 130.4 (d, J=10.9 Hz, PhC-meta), 130.5 (d, J=53.1 Hz,
PhB-ipso), 130.7 (d, J=2.2 Hz, PhB-para), 131.3 (d, J=
10.6 Hz, PhD-meta), 131.6 (d, J=2.2 Hz, PhA-para), 131.9 (d,
J=8.6 Hz, PhB-ortho), 132.8 (d, J=5.3 Hz, C11), 133.2 (d,
J=1.3 Hz, C7), 133.3 (d, J=8.9 Hz, PhD-ortho), 133.6 (d, J=
9.5 Hz, PhC-ortho), 133.8 (d, J=8.9 Hz, PhA-ortho), 136.4 (d,
J=5.4 Hz, C6), 158.8 (d, J=2.5 Hz, PhC-para), 159.4 (d, J=
2.6 Hz, PhD-para); 31P NMR (162 MHz, CDCl3): d=18.5 (bs,
C12-P), 24.7 (bs, C13-P); PhA and PhB connected to C12-P,
PhC and PhD connected to C13-P; HR-MS (ESI): m/z=
839.3195, calcd. for C49H56B2FeNaO2P2 [M+Na]+: 839.3206.
1aACHTUNGTRENNUNG(BH3)2–(R,Rp)–1dAHCUTNGTREN(NUGN BH3)2
To a stirred solution of aluminum chloride in THF (0.5M,
1.0 equiv.) was added a solution of lithium aluminium hy-
dride in THF (2.0M, 3.0 equiv.) at room temperature. Stir-
ring was continued for 30 min followed by the addition of
(R,Rp)-5aACHTUNGTRENNUNG(BH3)-(R,Rp)–5dCAHTUNGTRNE(NUGN BH3) (1.0 equiv.) dissolved in
THF (20 mL). After the evolution of gas had ceased the
mixture was heated under reflux for 30 min followed by the
addition of a solution of borane in THF (1.0M, 4.0 equiv.)
at room temperature. The reaction mixture was stirred for a
further 2 h and was subsquently quenched by the dropwise
addition of water. The product was extracted with EA (3ꢄ
100 mL) and the combined organic extracts were washed
with water and brine. After drying over MgSO4 and solvent
evaporation, the pure compounds were obtained by either
recrystallisation or column chromatography.
ACHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
3.63 mmol) the pure product was obtained after crystallisa-
tion from EA as orange needles suitable for X-ray diffrac-
tion; yield: 2.16 g (3.08 mmol, 85%); [a]2l0 (nm): +132.1
(589), +129.4 (578), +57.3 (546) (c 1.013, CHCl3); mp
1
2078C; H NMR (400 MHz, CDCl3): d=0.31–1.46 (bs, 6H,
C12-P-BH3 +C13-P-BH3), 1.70 (dd, J=16.2 Hz, J=7.3 Hz,
3H, CHCH3), 2.45 (dd, JH,H =14.5 Hz, JH,P =12.6 Hz, 1H,
CHAHB), 3.07 (dd,
J
H,H =14.5 Hz,
JH,P =10.8 Hz, 1H,
CHAHB), 3.54–3.57 (m, 1H, H2), 3.59–3.71 (m, 1H,
CHCH3), 3.98 (s, 5H, Cp’), 4.17–4.20 (m, 1H, H3), 4.48–4.52
(m, 1H, H4), 6.87 (bd, J=7.8 Hz, 1H, H10), 6.93–7.04 (m,
4H, PhC-ortho+PhC-meta), 7.11–7.28 (m, 4H, PhD-ortho+
PhC-para + H9), 7.31–7.40 (m, 5H, PhB-meta+PhD-meta+
H8), 7.40–7.54 (m, 6H, PhA-meta+PhA-para+PhB-ortho+
PhB-para), 7.57–7.66 (m, 3H, PhA-ortho+PhD-para), 7.85 (d,
J=7.7 Hz, 1H, H7); 13C NMR (100.6 MHz, CDCl3): d=19.3
(d, J=5.4 Hz, CHCH3), 27.1 (d, J=31.0 Hz, CHCH3), 30.4
(d, J=31.9 Hz, CHAHB), 66.7 (s, C3), 68.1–68.2 (m, C2+
C4), 70.2 (s, Cp’), 86.7 (s, C1), 89.7 (d, J=5.1 Hz, C5), 126.1
(d, J=2.6 Hz, C8), 126.4 (d, J=2.3 Hz, C9), 127.5 (d, J=
54.0 Hz, Ph-ipso), 128.1 (d, J=10.0 Hz, PhC-meta), 128.3,
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
(1.70 g, 2.38 mmol) the pure product was obtained after
crystallisation from EA as orange crystals. Crystals suitable
for X-ray diffraction were grown by slow diffusion of
hexane into a concentrated solution of the compound in
CDCl3; yield: 1.40 g (1.97 mmol, 83%); [a]2l0 (nm): +82.5
(589), +74.6 (578), +8.4 (546) (c 1.005, CHCl3); mp 2048C
1
(dec); H NMR (400 MHz, CDCl3): d=À0.42–0.54 (bd, 3H,
128.28, 128.77, 128.79 (Ph-ipso), 128.6 (d, J=9.8 Hz, PhA/B/D
-
C13-P-BH3), 0.70–1.75 (m, 25H, Cy+C12-P-BH3), 1.75 (dd,
J=14.1 Hz, J=7.4 Hz, 3H, CHCH3), 2.92–3.01 (m, 1H,
meta), 128.7 (d, J=9.3 Hz, PhA/B/D-meta), 128.8 (d, J=
9.7 Hz, PhA/B/D-meta), 130.3–130.4 (m, PhC-para+C10), 130.4
(d, J=53 Hz, Ph-ipso), 130.7 (d, J=2.2 Hz, PhB-para), 131.0
(d, J=2.3 Hz, PhA-para), 131.7 (d, J=2.2 Hz, PhD-para),
132.0 (d, J=8.5 Hz, PhD-ortho), 132.7 (d, J=8.5 Hz, PhB-
ortho+PhC-ortho), 132.8 (C11), 133.3 (d, J=1.5 Hz, C7),
133.8 (d, J=8.9 Hz, PhA-ortho), 136.5 (d, J=5.4 Hz, C6);
CHCH3), 3.43 (dd,
CHAHB), 3.75–3.79 (m, 1H, H2), 3.99 (s, 5H, Cp’), 4.05 (dd,
H,H =14.1 Hz, JH,P =10.8 Hz, 1H, CHAHB), 4.20–4.24 (m,
JH,H =14.1 Hz,
JH,P =12.8 Hz, 1H,
J
1H, H3), 4.30–4.33 (m, 1H, H4), 7.07–7.17 (m, 2H, H9+
H10), 7.28–7.34 (m, 1H, H8), 7.35–7.43 (m, 4H, PhB-ortho+
PhB-meta), 7.46–7.55 (m, 3H, PhA-meta+PhB-para), 7.57–
1070
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ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 1063 – 1074

Ferrocenyl-Aryl Based trans-Chelating Diphosphine Ligands
7.64 (m, 1H, PhA-para), 7.72–7.79 (m, 2H, PhA-ortho), 7.86
(d, J=7.8 Hz, 1H, H7); 13C NMR (100.6 MHz, CDCl3): d=
20.0 (d, J=2.3 Hz, CHCH3), 22.4 (d, J=25.4 Hz, CHCH3),
25.8 (d, J=6.6 Hz, Cy), 26.6–27.4 (m, Cy), 31.0 (d, J=
9.7 Hz, Cy), 31.3 (d, J=9.2 Hz, Cy), 31.9 (d, J=31.2 Hz,
CHAHB), 66.6 (s, C3), 67.8 (s, C4), 68.6 (s, C2), 70.3 (s, Cp’),
86.7 (s, C1), 92.3 (s, C5), 126.5 (d, J=2.4 Hz, C8), 126.7 (d,
J=2.1 Hz, C9), 127.4 (d, J=53.78 Hz, PhA-ipso), 128.7 (d,
J=9.6 Hz, PhA/B-meta), 128.9 (d, J=9.8 Hz, PhA/B-meta),
130.3 (d, J=52.9 Hz, PhB-ipso), 130.6 (d, J=3.8 Hz, C10),
130.8 (d, J=2.3 Hz, PhB-para), 131.9 (d, J=2.2 Hz, PhA-
para), 132.05 (d, J=8.7 Hz, PhB-ortho), 132.10 (d, J=5.4 Hz,
C11), 133.8 (d, J=1.2 Hz, C7), 134.0 (d, J=8.8 Hz, PhA-
ortho), 137.0 (d, J=5.3 Hz, C6); 31P NMR (162 MHz,
CDCl3): d=19.6 (bs, C12-P), 38.7 (bs, C13-P); PhA and PhB
connected to C12-P; HR-MS (ESI): m/z=735.3310, calcd.
for C43H56B2FeNaP2 [M+Na]+: 735.3290.
CHCH3), 2.75 (dd,
J
H,H =13.5 Hz,
JH,P =3.3 Hz, 1H,
CHAHB), 2.93 (d, JH,H =13.5 Hz, 1H, CHAHB), 3.28–3.37 (m,
1H, CHCH3), 4.06–4.10 (m, 1H, H4), 4.15–4.20 (m, 1H,
H3), 4.18 (s, 5H, Cp’), 4.38–4.41 (m, 1H, H2), 6.54–6.59 (m,
1H, H10), 6.91–6.97 (m, 2H, PhC-ortho), 6.98–7.05 (m, 3H,
PhC-meta+H9), 7.08–7.14 (m, 1H, PhC-para), 7.17–7.44 (m,
14H,
PhA-meta+PhA-para+PhB-ortho+PhB-meta+PhB-
para+PhD-ortho+PhD-meta+PhD-para+H8), 7.44–7.51 (m,
2H, PhA-ortho), 7.94 (d, J=7.4 Hz, 1H, H7); 13C NMR
(100.6 MHz, CDCl3): d=19.8 (d, J=14.6 Hz, CHCH3), 28.1
(d, J=14.8 Hz, CHCH3), 33.1 (dd, J=16.0 Hz, J=2.4 Hz,
CHAHB), 66.0 (s, C3), 66.2 (d, J=8.3 Hz, C4), 68.8 (d, J=
11.0 Hz, C2), 69.7 (s, Cp’), 88.4 (s, C1), 93.6 (d, J=18.3 Hz,
C5), 125.0 (d, J=2.6 Hz, C8), 126.2 (d, J=1.2 Hz, C9), 127.8
(s, PhC-para+PhD-para), 127.9 (d, J=6.2 Hz, PhC-meta),
128.0 (d, J=7.1 Hz, PhD-meta), 128.2 (d, J=5.3 Hz, PhB-
meta), 128.3 (d, J=7.2 Hz, PhA-meta), 128.8 (s, PhB-para),
129.2 (s, PhA-para), 129.8 (d, J=8.3 Hz, C10), 131.8 (d, J=
16.2 Hz, PhD-ortho), 132.8 (d, J=18.2 Hz, PhC-ortho), 133.4
(s, C7), 134.2 (d, J=20.2 Hz, PhB-ortho), 134.5 (d, J=
20.2 Hz, PhA-ortho), 136.3 (d, J=4.3 Hz, C6), 136.8 (d, J=
18.6 Hz, Ph-ipso), 137.1 (d, J=16.9 Hz, Ph-ipso), 137.6 (d,
J=8.0 Hz, C11), 137.7 (d, J=15.9 Hz, Ph-ipso), 139.6 (d, J=
16.6 Hz, Ph-ipso); 31P NMR (162 MHz, CDCl3): d=À8.4 (s,
C12-P), 7.6 (s, C13-P); PhA and PhB connected to C12-P,
PhC and PhD connected to C13-P; ESI-MS: m/z=673.3 [M+
H]+.
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
(1.40 g, 2.11 mmol) the pure product was obtained after
crystallisation from EA as yellow crystals; yield: 1.18 g
(1.79 mmol, 85%); [a]2l0 (nm): +89.3 (589), +79.6 (578),
+0.8 (546) (c 1.052, CHCl3); mp 1758C; 1H NMR
(400 MHz, CDCl3): d=À0.69–0.38 (bd, 3H, C12-P-BH3),
058–1.59 (m, 3H, C13-P-BH3), 0.84 [d, J=12.1 Hz, 9H, CB-
ACHTUNGTRENNUNG ACHTUNGTRENNUNG
(CH3)3], 1.24 [d, J=12.1 Hz, 9H, CA
J
J
General Procedure for the Synthesis of 1b–1d
J
A degassed solution of (R,Rp)-1bACHTUNRGTNEN(UG BH3)2-(R,Rp)–1dACHTUNGTRENNUNG(BH3)2
1H, H3), 4.25–4.29 (m, 1H, H4), 6.97–7.02 (m, 1H, H10),
7.03–7.09 (m, 1H, H9), 7.23–7.30 (m, 1H, H8), 7.34–7.51 (m,
7H, PhA-meta+PhB-meta+PhB-ortho+PhB-para), 7.53–7.59
(m, 1H, PhA-para), 7.71–7.79 (m, 2H, PhA-ortho), 7.79–7.84
(m, 1H H7); 13C NMR (100.6 MHz, CDCl3): d=22.6 (d, J=
2.5 Hz, CHCH3), 25.7 (d, J=20.8 Hz, CHCH3), 28.2 [s, CB-
(2.0 mmol) in morpholine (20 mL) was heated for 3 h at
1008C. After cooling, the solvent was removed under re-
duced pressure and the crude product was taken up in de-
gassed diethyl ether (50 mL). The organic phase was washed
with a degassed aqueous citric acid (5%, 20 mL) and de-
gassed brine. After drying over MgSO4 and removal of the
solvent under reduced pressure, the crude product was puri-
fied by column chromatography under inert conditions.
G
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
Cp’), 87.9 (s, C1), 94.0 (d, J=4.8 Hz, C5), 126.0 (d, J=
2.5 Hz, C8), 126.3 (d, J=2.1 Hz, C9), 128.1 (d, J=53.9 Hz,
PhA-ipso), 128.6 (d, J=9.8 Hz, PhB-meta), 128.7 (d, J=
9.9 Hz, PhA-meta), 130.6–130.7 (m, PhB-para+C10), 130.8
(d, J=53.6 Hz, PhB-ipso), 131.5 (d, J=2.2 Hz, PhA-para),
132.1 (d, J=8.5 Hz, PhB-ortho), 133.0 (d, J=4.6 Hz, C11),
133.4 (d, J=1.2 Hz, C7), 133.9 (d, J=9.0 Hz, PhA-ortho),
137.4 (d, J=5.4 Hz, C6); 31P NMR (162 MHz, CDCl3): d=
19.1 (bs, C12-P), 57.9 (bs, C13-P); PhA and PhB connected to
C12-P; HR-MS (ESI): m/z=660.3080, calcd. for
C39H52B2FeP2 [M]+: 660.3094.
AHCTUNGTRENNUNG
2.24 mmol) the pure product was obtained as a yellow foam
after column chromatography on aluminum oxide 90 using
PE/EA=5/1 as the eluent; yield: 1.35 g (1.71 mmol, 76%);
[a]2l0 (nm): +176.9 (589), +173.8 (578), +130.5 (546) (c
1
1.024, CHCl3); mp 618C; H NMR (400 MHz, CDCl3): d=
1.56 (dd, J=12.6 Hz, J=7.1 Hz, 3H, CHCH3), 2.02 (s, 6H,
PhD-CH3), 2.24 (s, 6H, PhC-CH3), 2.63 (dd, JHH =13.4 Hz,
J
HP =3.5 Hz, 1H, CHAHB), 2.83 (d,
JHH =13.4 Hz, 1H,
CHAHB), 3.25–3.34 (m, 1H, CHCH3), 3.60 (s, 3H, PhD-
OCH3), 3.72 (s, 3H, PhC-OCH3), 4.11–4.14 (m, 1H, H4),
4.19 (s, 5H, Cp’), 4.19–4.21 (m, 1H, H3), 4.42–4.45 (m, 1H,
H2), 6.44–6.49 (m, 1H, H10), 6.61 (d, J=7.4 Hz, 2H, PhD-
ortho), 6.99 (d, J=7.3 Hz, 2H, PHC-ortho), 6.97–7.03 (m,
1H, H9), 7.20–7.34 (m, 6H, H8+PhB-ortho+PhB-meta+
PhB-para), 7.34–7.44 (m, 3H, PhA-meta+PhA-para), 7.44–
7.51 (m, 2H, PhA-ortho), 7.93 (d, J=7.5 Hz, 1H, H7);
13C NMR (100.6 MHz, CDCl3): d=16.1 (s, PhC/D-CH3), 16.1
(s, PhC/D-CH3), 20.1 (d, J=16.0 Hz, CHCH3), 28.3 (d, J=
13.6 Hz, CHCH3), 32.6 (d, J=17.9 Hz, CHAHB), 59.3 (s,
PhD-OCH3), 59.6 (s, PhC-OCH3), 65.9 (s, C3), 66.2 (d, J=
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
(150 mL) was stirred for 16 h at room temperature. The sol-
vent was removed under reduced pressure and the crude
product was purified by chromatography on aluminum
oxide 90 under inert conditions (eluent: PE/DCM=1/1) to
give the title compound as a yellow foam; yield: 1.64 g
(2.43 mmol, 79%); [a]2l0: (nm): +173.1 (589), +169.2 (578),
+118.7 (546) (c 1.026, CHCl3); mp 568C; 1H NMR
(400 MHz, CDCl3): d=1.57 (dd, J=12.1 Hz, J=7.1 Hz, 3H,
Adv. Synth. Catal. 2010, 352, 1063 – 1074
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1071

Raffael Schuecker et al.
FULL PAPERS
7.9 Hz, C4), 68.6 (d, J=12.1 Hz, C2), 69.7 (s, Cp’), 88.2 (s,
C1), 94.1 (d, J=20.0 Hz, C5), 124.8 (d, J=2.4 Hz, C8), 125.9
(d, J=1.6 Hz, C9), 127.8 (s, PhB-para), 128.17, 128.22,
128.26, 128.34 (PhA-meta+PhB-meta), 129.2 (s, PhA-para),
129.6 (d, J=7.9 Hz, C10), 130.0 (d, J=7.7 Hz, PhD-meta),
130.3 (d, J=8.1 Hz, PhC-meta), 131.7 (d, J=16.5 Hz, PhB-
ortho), 133.4 (s, C7), 133.9 (d, J=20.0 Hz, PhD-ortho), 134.5
(d, J=21.2 Hz, PhC-ortho), 134.6 (d, J=20.4 Hz, PhA-ortho),
136.3 (d, J=4.4 Hz, C6), 137.5 (d, J=8.5 Hz, C11), 137.8 (d,
J=15.6 Hz, PhA-ipso), 139.6 (d, J=16.7 Hz, PhB-ipso), 157.2
(s, PhD-para), 157.7 (s, PhC-para), PhC-ipso+PhD-ipso not
observed; 31P NMR (162 MHz, CDCl3): d=À8.9 (s, C12-P),
7.1 (s, C13-P); PhA and PhB connected to C12-P, PhC and
PhD connected to C13-P; ESI-MS: m/z=789.4 [M+H]+.
ortho+PhB-meta+PhB-para), 7.30–7.37 (m, 3H, PhA-meta+
PhA-para), 7.47–7.54 (m, 2H, PhA-ortho), 7.39 (d, J=7.4 Hz,
1H, H7); 13C NMR (100.6 MHz, CDCl3): d=17.9 (d, J=
2.0 Hz, CHCH3), 28.5 (d, J=35.0 Hz, CHCH3), 30.2 [d, J=
14.0 Hz, CB
J=29.0 Hz, CB
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
(dd, J=15.0 Hz, J=11.4 Hz, CHAHB), 64.9 (s, C3), 66.3 (d,
J=1.2 Hz, C4), 69.4 (s, Cp’), 70.0 (d, J=7.9 Hz, C2), 90.1 (d,
J=3.8 Hz, C1), 96.9 (d, J=25.8 Hz, C5), 125.1 (d, J=2.4 Hz,
C8), 126.6 (s, C9), 127.8 (s, PhA/B-para), 128.09, 128.14, 128.2,
128.3 (PhA-meta+PhB-meta), 128.8 (s, PhA/B-para), 129.4 (d,
J=11.1 Hz, C10), 132.1 (d, J=16.8 Hz, PhB-ortho), 133.9 (s,
C7), 134.2 (d, J=19.9 Hz, PhA-ortho), 137.00 (d, J=4.5 Hz,
C6), 138.6 (d, J=15.4 Hz, PhA-ipso), 139.2 (d, J=9.7 Hz,
C11), 140.1 (d, J=16.0 Hz, PhB-ipso); 31P NMR (162 MHz,
CDCl3): d=À11.1 (s, C12-P), 48.6 (s, C13-P); PhA and PhB
connected to C12-P; ESI-MS: m/z=633.4 [M+H]+.
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
was obtained as a yellow foam after column chromatogra-
phy on aluminum oxide 90 using PE/DEE=5/1 as the
eluent; yield: 915 mg (1.34 mmol, 68%); [a]2l0 (nm): +103.9
(589), +99.2 (578), +53.4 (546) (c 1.195, CHCl3); mp 658C;
1H NMR (400 MHz, CDCl3): d=0.53–1.72 (m, 22H, Cy),
1.61 (dd, J=9.8 Hz, J=7.4 Hz, 3H, CHCH3), 2.68–2.78 (m,
1H, CHCH3), 3.22 (dd, JH,H =13.7 Hz, JH,P =3.3 Hz, 1H,
CHAHB), 3.46 (d, JH,H =13.7 Hz, 1H, CHAHB), 4.14–4.21 (m,
2H, H4+H3), 4.17 (s, 5H, Cp’), 4.41–4.44 (m, 1H, H2),
6.64–6.71 (m, 1H, H10), 6.95–7.02 (m, 1H, H9), 7.14–7.31
(m, 1H, H8), 7.22–7.28 (m, 5H, PhB-ortho+PhB-meta+PhB-
para), 7.32–7.39 (m, 3H, PhA-meta+PhA-para), 7.50–7.56
(m, 2H, PhA-ortho), 7.90 (bd, J=7.5 Hz, 1H, H7); 13C NMR
(100.6 MHz, CDCl3): d=19.5 (d, J=11.4 Hz, CHCH3), 23.9
(d, J=23.1 Hz, CHCH3), 26.4 (d, J=13.4 Hz, Cy), 27.1–27.6
(m, Cy), 29.5 (d, J=11.4 Hz, Cy), 30.4 (d, J=4.3 Hz, Cy),
30.5 (d, J=2.7 Hz, Cy), 31.0 (d, J=20.2 Hz, Cy), 31.5 (d, J=
16.9 Hz, Cy), 32.2 (d, J=19.7 Hz, Cy), 33.9 (dd, J=16.4 Hz,
J=4.8 Hz, CHAHB), 65.5 (s, C3/C4), 65.7 (d, J=2.9 Hz, C3/
C4), 69.3 (d, J=10.0 Hz, C2), 69.7 (s, Cp’), 88.6 (d, J=
1.6 Hz, C1), 96.1 (d, J=13.2 Hz, C5), 125.1 (d, J=2.3 Hz,
C8), 126.3 (s, C9), 127.8 (s, PhA/B-para), 128.2 (d, J=5.2 Hz,
X-ray Structure Determination for Compounds
(R,Rp)-1a
5c(BH3)
ACHTUTNGRNE(NGU BH3)2, (R,Rp)-1cACHTUNGTNERN(UGN BH3)2, and (R,Rp)-
AHCTUNGTRENNUNG
X-ray data were collected on a Bruker Smart APEX CCD
area detector diffractometer using graphite-monochromated
Mo-Ka radiation (l=0.71073 ꢅ) and 0.38 w-scan frames.
Corrections for absorption and l/2 effects were applied.[28]
.
The structures were solved with the program SHELXS97
and direct methods, refinement on F2 was carried out with
the program SHELXL97.[29] Non-hydrogen atoms were re-
fined anisotropically. All H atoms were placed in calculated
positions and thereafter treated as riding. The absolute
structures could be unambiguously determined by anoma-
lous dispersion effects and the Flack absolute structure pa-
rameter (FASP). Important crystallographic data are:
A
ACHTNUGRTNE(NUGN BH3)2 as the ethyl acetate solvate (R,Rp)-1a-
AHCTUNGTRENNUNG
plate from ethyl acetate/pentane, 0.45ꢄ0.36ꢄ0.12 mm, mon-
oclinic, space group P21 (no. 14), a=10.6789(8) ꢅ, b=
10.4268(8) ꢅ,
c=19.0090(15) ꢅ,
b=90.140(2)8,
V=
PhA/B-meta), 125.4 (d, J=7.2 Hz, PhA/B-meta), 129.2 (s, PhA/B
-
2116.6(3) ꢅ3, Z=2, m =0.469 mmÀ1, dx =1.237 gcmÀ3, T=
100 K. 45361 reflections collected (qmax =30.08) and merged
to 12228 independent data (Rint =0.023); final R indices (all
data): R1 =0.0328, wR2 =0.0863, 489 parameters, FASP=
À0.004(7).
para), 129.8 (d, J=9.2 Hz, C10), 131.8 (d, J=16.2 Hz, PhB-
ortho), 133.7 (s, C7), 134.6 (d, J=20.4 Hz, PhA-ortho), 136.7
(d, J=4.5 Hz, C6), 137.8 (d, J=8.6 Hz, C11), 137.9 (d, J=
15.5 Hz, PhA-ipso), 139.8 (d, J=16.8 Hz, PhB-ipso);
31P NMR (162 MHz): d=À8.9 (s, C12-P), 20.8 (s, C13-P);
PhA and PhB connected to C12-P; ESI-MS: m/z=685.4 [M+
H]+.
AHCTUNRGENNU(G R,Rp)-1cACHTUNGTRNEN(UGN BH3)2: C43H56B2FeP2, Mr =712.29, orange oval
from CDCl3/hexane, 0.60ꢄ0.56ꢄ0.34 mm, orthorhombic,
space group P212121 (no. 19), a=11.0256(9) ꢅ, b=
11.4431(10) ꢅ, c=30.080(3) ꢅ, V=3795.1(6) ꢅ3, Z=4, m
=0.511 mmÀ1, dx =1.247 gcmÀ3, T=100 K. 49447 reflections
collected (qmax =30.08) and merged to 11035 independent
data (Rint =0.022); final R indices (all data): R1 =0.0236,
wR2 =0.0615, 436 parameters, FASP =0.004(6).
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
was obtained as a yellow foam after column chromatogra-
phy on aluminum oxide 90 using PE/DEE=1/1 as the
eluent; yield: 820 mg (1.24 mmol, 73%); [a]2l0 (nm): +63.8
(589), +57.1 (578), +1.5 (546) (c 1.023, CHCl3); mp 638C;
1H NMR (400 MHz, CDCl3): d=0.75 [d, J=10.5 Hz, 9H,
AHCNTUGERNNU(G R,Rp)-1cACHTUNTGRNE(NUNG BH3)2: C43H53BFeOP2, Mr =714.45, orange
block from CHCl3/hexane, 0.46ꢄ0.44ꢄ0.29 mm, orthorhom-
bic, space group P212121 (no. 19), a=11.6864(7) ꢅ, b=
14.5906(9) ꢅ, c=22.4467(14) ꢅ, V=3827.4(4) ꢅ3, Z=4, m
=0.510 mmÀ1, dx =1.240 gcmÀ3, T=100 K. 51921 reflections
collected (qmax =30.08) and merged to 11161 independent
data (Rint =0.023); final R indices (all data): R1 =0.0225,
wR2 =0.0587, 435 parameters, FASP =À0.003(5).
CB(CH3)3], 1.13 [d, J=10.6 Hz, 9H, CA
ACHTUNGTRENNUNG ACHTUNTGREN(NUGN CH3)3], 1.84 (dd, J=
7.4 Hz, J=3.3 Hz, 3H, CHCH3), 2.75–2.84 (m, 1H,
CHCH3), 3.31 (dd, JHH =14.6 Hz, JHP =3.6 Hz, 1H, CHAHB),
3.39 (d, JH,H =14.6 Hz, 1H, CHAHB), 4.14–4.17 (m, 1H, H3),
4.18–4.20 (m, 1H, H4), 4.23 (s, 5H, Cp’), 4.31–4.33 (m, 1H,
H2), 6.72–6.78 (m, 1H, H10), 7.00 (dd, J=7.5 Hz, J=1.3 Hz,
1H, H9), 7.13–7.20 (m, 1H, H8), 7.22–7.30 (m, 5H, PhB-
Crystallographic data (excluding structure factors) for the
structures reported in this paper have been deposited with
1072
asc.wiley-vch.de
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 1063 – 1074

Ferrocenyl-Aryl Based trans-Chelating Diphosphine Ligands
the Cambridge Crystallographic Data Centre as supplemen-
tary publication nos. CCDC 753637, CCDC 753638 and
CCDC 753639. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif or on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax.:
(internat.) +44 1223/336–033; e-mail: deposit@ccdc.cam.
ac.uk].
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