Synthesis of ferrocene-based phosphine ligands via Cu-catalyzed reductive coupling of ferrocenyl ketone-derived tosylhydrazones and H-phosphorus oxides

Article abstract of DOI:10.1016/j.tet.2016.11.054

Ferrocene-based phosphine oxides with various substituents at phosphorous atoms were synthesized by Cu-catalyzed reductive coupling of ferrocenyl ketone-derived tosylhydrazones and H-phosphorus oxides. Followed by the reduction of ferrocene-based phosphin

Full text of DOI:10.1016/j.tet.2016.11.054

Accepted Manuscript
Synthesis of ferrocene-based phosphine ligands via Cu-catalyzed reductive coupling
of ferrocenyl ketone-derived tosylhydrazones and H-phosphorus oxides
Li Ling, Jianfeng Hu, Yanhong Huo, Hao Zhang
PII:
S0040-4020(16)31218-2
10.1016/j.tet.2016.11.054
TET 28268
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 21 October 2016
Revised Date: 17 November 2016
Accepted Date: 21 November 2016
Please cite this article as: Ling L, Hu J, Huo Y, Zhang H, Synthesis of ferrocene-based phosphine
ligands via Cu-catalyzed reductive coupling of ferrocenyl ketone-derived tosylhydrazones and H-
phosphorus oxides, Tetrahedron (2016), doi: 10.1016/j.tet.2016.11.054.
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Synthesis of Ferrocene-based Phosphine
Ligands via Cu-catalyzed Reductive
Leave this area blank for abstract info.
Coupling of Ferrocenyl Ketone-derived
Tosylhydrazones and H-phosphorus Oxides
Li Ling,a,b Jianfeng Hu,a,b Yanhong Huo,a Hao Zhanga,b,c
a School of Chemistry & Chemical Engineering, Inner Mongolia University, Hohhot 010021, P. R. China
b Inner Mongolia Key Laboratory of Fine Organic Synthesis, Hohhot 010021, P. R. China
c State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese
Academy of Sciences, Changchun 130022, P. R. China

1
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Tetrahedron
journal homepage: www.elsevier.com
Synthesis of Ferrocene-based Phosphine Ligands via Cu-catalyzed Reductive
Coupling of Ferrocenyl Ketone-derived Tosylhydrazones and H-phosphorus Oxides
Li Linga,b , Jianfeng Hua, b , Yanhong Huoa , Hao Zhanga,b,c
a School of Chemistry & Chemical Engineering, Inner Mongolia University, Hohhot 010021, P. R. China
b Inner Mongolia Key Laboratory of Fine Organic Synthesis, Hohhot 010021, P. R. China
c State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R.
China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Ferrocene-based phosphine oxides with various substituents at phosphorous atoms were
synthesized by Cu-catalyzed reductive coupling of ferrocenyl ketone-derived tosylhydrazones
and H-phosphorus oxides. Followed by the reduction of ferrocene-based phosphine oxides, 1-
substituted ferrocene-based phosphine ligand 7 and 1,1’-disubstituted ferrocene-based phosphine
ligand 9 were obtained. Josiphos type ligand 8 were produced after ortho-lithiation of 7 and
trapping with chlorodiphenyl phosphine or chlorodicyclohexylphosphine.
Available online
Keywords:
ferrocene
2009 Elsevier Ltd. All rights reserved
.
phosphine ligand
tosylhydrazone
Cu-catalyzed
H-phosphorus Oxide
1. Introduction
Since its discovery in 1951, ferrocene has been among the
most important structural motifs in ligand architectures due to its
high thermal stability, conformational rigidity and planar
chirality.1 Ferrocene-based phosphine ligands are of fundamental
importance in transition metal-catalyzed organic reactions.2
Achiral
ferrocene
phosphine
such
as
1,1’-bis
(diphenylphosphino) ferrocene (DPPF),3 has been successfully
applied in transition-metal catalyzed coupling reactions.4
Moreover, chiral ferrocene-based phosphine ligands have become
indispensable and powerful tools for chemists in dealing with
asymmetric transformations.2,5 Some of them, such as Josiphos6
Fig. 1. Representative ferrocene-based phosphine ligands.
and
N,N-dimethyl-1-[2-
Recently, N-tosylhydrazones which are readily prepared from
carbonyl compounds have been used as a source of the safe
generation of diazo compounds and carbenes.10 They have
emerged as a new type of cross-coupling partner in C-C(X) bond
formation including their reactions with aryl halides,11
(diphenylphosphino)ferrocenyl]ethylamine (PPFA)7, have found
their industrial application in the production of pharmaceuticals
and agrochemicals. Selected examples of chiral and achiral
ferrocene phosphine ligands are shown in Figure 1. These chiral
ferrocene phosphine ligands are all prepared from N,N-dimethyl-
1-ferrocenylethylamine (Ugi's amine)8 as a chiral precursor.
Despite their wide application, synthesis of ferrocene phosphine
ligands often requires sensitive reagents, tedious synthetic routes
and resolution steps.9 Therefore, inexpensive and readily
available starting materials, as well as short synthetic steps are
most desirable in designing new ferrocene-based phosphine
arylsulfonates,12
alkynes,13
H-phosphonates,14
azoles,15
arylboronic acids,16 benzylic halides.17,18
19
Inspired by our previous work,
in this paper we have
synthesized 1-substituted and 1,1’-disubstituted ferrocene-based
phosphine oxides from readily available ferrocenyl
ketone/aldehyde derived tosylhydrazones and secondary
phosphine oxides without using sensitive reagents. Moreover, the
ligands.
———
Corresponding author. Tel.: +86 471 4994406; fax: +86 471 4994406; e-mail: haozhang@imu.edu.cn

2
Tetrahedron
d
trimethylphenyl)-2-imidazolidinylidene. The reaction temperature was
ferrocene-based phosphine oxides can be readily converted to the
corresponding ferrocene-based phosphine through reduction
treatment20,21 and as useful ligands for transition metal complexes.
ACCEPTED MANUSCRIPT
90oC.
Table 2
Reaction of various ferrocenyl ketone-derived N-tosylhydrazones with H-
phosphorus oxides and H-phosphonates a,b
2. Results and discussion
Initially, tosylhydrazone 1a and diphenylphosphine oxide 2a
were chosen as the model substrates to screen the best reaction
conditions (Table 1). To our delight, CuCl was found to promote
the reaction between 1a and 2a in dioxane with K2CO3 as base at
reflux temperature for 12
h to produce diphenyl (1-
ferrocenylethyl) phosphine oxide 3a in 61% yield (Table 1, entry
1). 1H, 31P and 13C NMR spectra of 3a was consistent with
literature reported.22 After screening several kind of Cu catalysts,
CuI was found to be the most efficient compared to others (Table
1, entries 1-5). Various bases, such as K2CO3, Cs2CO3, Na2CO3,
KOH, LiOtBu and KOtBu were tested. K2CO3 gave the highest
yield of 3a (Table 1, entries 5-10). Changing the solvent under
identical condition resulted in the decreased formation of 3a
(Table 1, entries 11−15). When the amount of diphenylphosphine
oxide was increased, 3a’s yield dramatically decreased (Table 1,
entry 16). This outcome was also observed when the reaction was
carried out at lower reaction temperature of 90 oC (Table 1, entry
17). In the control experiment, no product 3a was detected under
metal-free condition (Table 1, entry 18). Thus, the optimized
condition was obtained as the following: 10 mol % of CuI, 3
equivalent of K2CO3, in dioxane and reflux under argon (Table 1,
entry 5).
Table 1
Optimization of reaction conditionsa
catalyst
(mol%)
base
(equiv.)
yieldb
(%)
entry 1a:2a
solvent
1
2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:2
CuCl(10%)
CuCl2(10%)
CuBr(10%)
SIMesCuCl(10%)c
CuI(10%)
CuI(10%)
CuI(10%)
CuI(10%)
CuI(10%)
CuI(10%)
CuI(10%)
CuI(10%)
CuI(10%)
CuI(10%)
CuI(10%)
CuI(10%)
CuI(10%)
—
K2CO3(3)
K2CO3(3)
K2CO3(3)
K2CO3(3)
K2CO3(3)
Cs2CO3(3)
Na2CO3(3)
KOH(3)
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
DME
61
56
35
0
3
4
5
83
44
7
6
7
8
24
20
0
9
LiOtBu(3)
KOtBu(3)
K2CO3(3)
K2CO3(3)
K2CO3(3)
K2CO3(3)
K2CO3(3)
K2CO3(3)
K2CO3(3)
K2CO3(3)
10
11
12
13
14
15
16
17d
18
30
15
35
28
31
19
56
0
DMF
DCE
THF
toluene
dioxane
dioxane
dioxane
1:1.2
1:1.2
a Reactions were carried out with 0.25 mmol of 1a and 0.30 mmol of 2a
in the presence of catalyst and base under argon atmosphere at reflux
temperature for 12 h. bYield of isolated product. cSIMes = 1,3-bis(2,4,6-
a Reactions were carried out with 0.25 mmol of 1a-g and 0.30 mmol of 2a-h
in the presence of 10 mol% of CuI and 3.0 equivalent of K2CO3 at reflux

3
temperature under argon atmosphere for 12 h. b Yield of isolated product after
ACCEPTED MANUSCRIPT
chromatography.
Table 3
With this optimized reaction condition in hand, the scope of
the reaction was studied using a set of tosylhydrazones 1 and H-
phosphorus oxides or H-phosphonates 2 (Table 2). Various
ferrocenyl ketones or aldehyde derived tosylhydrazones were
investigated. Steric hindrance of ferrocenyl ketones dramatically
decreased production yields (3a-e). Electron-withdrawing group
(-F) on phenyl ring of H-phosphorus oxide decreased the reaction
efficiency to some extent (3u), while electron-donating groups (-
CH3, -OCH3) on phenyl ring of H-phosphorus oxides increased
production yields, generating product 3t and 3v in 94%, 81%
yields. Bis(3,5-dimethylphenyl)phosphine oxide reacted with
ferrocenyl ketones derived tosylhydrazones to give products 3g–
3k in moderate to good yields, while bis(2,6-
dimethylphenyl)phosphine oxide led to low yield (3w) due to
steric hindrance. Moreover, ethyl phenylphosphinate or diethyl
phosphonate could also be used as substrates generating
corresponding products (3l-3s) in 49-84% yields. Finally, the
molecular structure of 3u (Figure 2) and 3w (Figure 3) were
unambiguously confirmed through X-ray crystallography.
Reaction of various 1,1’-ferrocenyl di-ketone-derived N-
tosylhydrazones 4a-e with H-phosphorus oxides and ethyl
phenylphosphinatea
Fig. 2. Molecular structure of 3u with thermal ellipsoids drawn at the 30%
probability level, and hydrogen atoms are omitted for clarity. Selected bond
lengths (Å) and angles (deg): P1-O1 = 1.484(3), P1 - C18 = 1.797(4), P1-
C11 = 1.833(4), P1 - C12 = 1.810(4), C9 -C11 = 1.494(6); C9 - C11-P1 =
109.0(3), C12-P1-C11 = 104.9(2), O1-P1-C11 = 113.98(18), C18-P1-C12 =
105.55(17), C18-P1-C11 = 109.39(18).
a Reactions were carried out with 0.15 mmol of 4a-e and 0.36 mmol of 2a-f in
the presence of 20 mol% of CuI and 6.0 equivalent of K2CO3 at reflux
temperature under argon atmosphere for 18 h.
Single crystals suitable for X-ray diffraction measurement
were obtained by slow diffusion of hexane into a concentrated
dichloromethane solution of compounds. Crystals of compound
3u were twinned and contain two independent molecules of
enantiomers. The ORTEP representation of the structure shows
that the planes of the cyclopentadienyl rings are almost parallel to
each other (tilt angles are 2.2°(S) and 4.4°(R) for the two
independent molecules of 3u, 4.9° for 3w,). Carbon atom linked
to the Cp ring is almost coplanar with the substituted Cp ring.
Bulkier diphenylphosphinyl moiety is located farther away from
the Cp ring. This phenyl ring is almost orthogonal to another
phenyl ring, the dihedral angles between them are 74.2°(S),
69.9°(R) for 3u and 83.5° for 3w. The phosphorus oxygen
distance is 1.484(3) (S) and 1.492(3) (R) for the two independent
molecules of 3u and 1.492(3) in 3w, typical for a P-O double
bond. The bond length of C-P in 3w (1.839(17)-1.856(17) Å) is
longer than that of the corresponding C-P bond (1.797(4)-1.833(4)
Fig. 3. Molecular structure of 3w with thermal ellipsoids drawn at the 30%
probability level, and hydrogen atoms are omitted for clarity. Selected bond
lengths (Å) and angles (deg): P1-O1 = 1.4924(13), P1 - C19 = 1.8560(17),
P1- C10 = 1.8523(17), P1 - C11 =1.8394(17), C9 -C10 = 1.517(2); C9 - C10-
P1 = 107.16(12), C11-P1-C10 = 105.87(8), O1-P1-C10 = 107.61(8), C11-P1-
C19 = 108.11(7), C10-P1-C19 = 114.46(8).

4
Tetrahedron
ACCEPTED MANU
Å) (S) and (1.794(4)-1.826(4) Å) (R) in 3u, which is well
1
SCRIPTL1
71
50:50
50:50
50:50
50:50
45:55
46:54
—
explained by the increased steric hindrance of ortho methyl
substituted phenyl groups around P1 in 3w. The shortest distance
between the corresponding atoms H18 and O1 is 242.2 pm in 3w,
which is smaller than the sum of the van der Waals radii of these
elements (272 pm).23 The bond angles around phosphorus are
107.9(2)-114.0(18)° (S) and 106.1(17)-114.2(16)° (R) for 3u and
105.9(8)-114.5(8)° for 3w, similar to the ones (104.8(13)-
113.2(13)°) reported for [1-(1-naphthalenyl)ethyl] diphenyl-
phosphine oxide.24
2
3
4
5
6
7
8
L2
L3
L4
L5
L6
L7
L8
76
32
22
75
78
trace
24
50:50
a Reaction conditions: 1a (0.25 mmol), 2a (0.30 mmol), CuI (10mol %),
ligand (12 mol %), K2CO3 (3.0 equiv.) in dioxane under argon at reflux
temperature for 12 h. b Isolated yield. c Determined by HPLC analysis.
Inspired by these results, we delightfully found that product 5a
was generated in 65% yield through the reaction of 1,1’-
ferrocenyl di-ketone-derived N-tosylhydrazone 4a with
diphenylphosphine oxide by extending reaction time.
Interestingly, byproduct 6 were produced at the same time and 6a
was isolated in 31% yield (Table 3). The reaction displayed the
similar steric and electron effect with the reductive coupling of
ferrocenyl ketone derived tosylhydrazones 1 with H-phosphorus
oxides and ethyl phenylphosphinate 2 (Table 3).
Furthermore, 1-substituted ferrocenyl phosphines ligand 7 and
1,1’-bis-substituted ferrocenyl phosphines ligand
9
were
produced in good yield by reduction of (P=O) bond. Josiphos
type ligand 8 were synthesized in moderate yield through ortho-
lithiation of Cp ring of 7 followed by reaction with Ph2PCl or
Cy2PCl (Scheme 1).
3. Conclusions
Scheme 1. Synthesis of 1-substituted, 1,2- disubstituted and 1,1’-disubstituted
ferrocenyl phosphine ligands.
In summary, Cu-catalyzed reductive coupling of ferrocenyl
ketone tosylhydrazones and H-phosphorus oxides or H-
phosphonates was shown to be a practical and efficient method
for the synthesis of ferrocene-based phosphine ligands in
moderate to good yields. 1-substituted, 1,2- and 1,1’-bis-
substituted ferrocenyl phosphine ligands could be obtained from
this procedure, which is of operational simplicity and functional
group tolerance. Research on synthesis of chiral ferrocenyl
phosphine oxides through enantioselective Cu-catalyzed
reductive coupling reaction is under way.
For further application of this approach to chiral ferrocenyl
phosphine ligands, we examined various types of chiral ligands
to induce enantioselectivity (Table 4). Tridentate chiral oxazoline
pyridine ligand L1, gave 71% yield of racemic 3a (entry 1). No
improvement was observed with bidentate oxazoline ligand L2
and spiral bidentate oxazoline ligand L3 (entry 2 and entry 3).
Monodentate phosphoramidite ligand like TADDOL-derived
phosphoamidite L4 was also examined and showed no
enantioselectivity (entry 4). Although, the enantioselectivity
increased a little to 45:55 er with a yield of 78% when axial
chiral diphosphine (S)-BINAP (L5) was added (entry 5). Other
axial chiral diphosphine like synphos (L6) did not afford better
result (entry 6). Planar chiral diphosphine Josiphos (L7) and P-
stereogenic diphosphine (L8) had low catalytic and
enantioselective activity (entry 7 and entry 8). The reason for low
enantioselectivity was probably the high reaction temperature,
since the diazo compounds were generated in situ from
tosylhydrazone in the presence of base and thermal condition.
4. Experimental section
4.1. General Experimental Methods:
All reactions were carried out in oven dried glassware under
argon unless otherwise specified. All NMR experiments were
carried out on a Bruker AVANCE 500MHz nuclear magnetic
resonance spectrometer using CDCl3 or DMSO-d6 as the solvent
with tetramethylsilane as the internal standard (31P NMR with
85% H3PO4 as the external standard). Chemical shift values (δ)
were given in parts per million. HRMS data were obtained on a
Bruker QTOF mass mass spectrometer. The melting points were
determined on an X-4 binocular microscope melting point
apparatus and uncorrected. HPLC analyses were performed on a
LC-20A instrument using Chiralpak® AD-H columns (0.46cm
Diameter x 25cm Length). THF, DCE, dioxane, toluene, DMF
and DME were dried according to literature techniques.
Table 4
Asymmetric Cu-catalyzed reductive coupling reactiona
entry
ligand
yield (%)b
erc

5
4.2. General Procedure for Copper-catalyzed Reductive
Coupling of Ferrocenyl Ketone-derived N-tosylhydrazones with
H-phosphorus Oxides and H-phosphonates:
69.46 (s, Cp), 68.49 (s, Cp’), 67.98 (s, Cp), 67.50 (s, Cp), 66.84
ACCEPTED MANUSCRIPT
(s, Cp), 40.80 (d, JC-P = 65.4 Hz, CHCH2CH2CH3), 32.30 (s,
CHCH2CH2CH3), 22.92 (d, JC-P = 4.6 Hz, CHCH2CH2CH3),
14.46 (s, CHCH2CH2CH3); 31P{1H} NMR (202 MHz, CDCl3) δ
33.94. HRMS (ESI-TOF) m/z: [M]+ calcd for C26H27FeOP
442.1149; Found: 442.1142.
0.30 mmol H-phosphorus oxide or H-phosphonate, 0.25 mmol
N-Tosylhydrazone, 0.025mmol of CuI and 0.75 mmol K2CO3
were charged into 25 mL oven-dried flasks, and backfilled with
Argon three times. 3 mL freshly distilled 1,4-dioxane was then
injected into the flask, which were heated up to reflux for 12 h.
The solvent was eliminated under vacuum pump and ammonia
water and dichloromethane was added and the layers were
separated. The aqueous phase was extracted three times with
dichloromethane. The combined organic phase was dried over
Na2SO4. The concentrated residue was purified by column
chromatography over silica gel using petroleum ether/ethyl
acetate (1:3) as eluent to get the product.
4.2.1. Diphenyl(1-ferrocenylethyl)phosphine oxide (3a).22 Yellow
solid, 85.5 mg (83% yield); mp 155 – 156oC; Rf (petroleum
ether/ethyl acetate 1:3) = 0.5. 1H NMR (500 MHz, CDCl3) δ 7.83
– 7.71 (m, 2H, P(O)Ph2), 7.58 – 7.39 (m, 6H, P(O)Ph2), 7.29 –
7.38 (m, 2H, P(O)Ph2), 4.18 – 4.08 (m, 6H, Cp and Cp’), 4.08 –
4.05 (m, 1H, Cp), 3.95 – 3.87 (m, 1H, Cp), 3.54 – 3.45 (m, 1H,
4.2.4. (2-Methyl-1-ferrocenylpropyl)diphenylphosphine oxide
(3d). Yellow solid, 78.7 mg (71% yield); mp 211 – 212oC; Rf
1
(petroleum ether/ethyl acetate 1:2) = 0.6. H NMR (500 MHz,
CDCl3) δ 7.80 – 7.67 (m, 2H, P(O)Ph2), 7.59 – 7.51 (m, 2H,
P(O)Ph2), 7.51 – 7.37 (m, 4H, P(O)Ph2), 7.37 – 7.29 (m, 2H,
P(O)Ph2), 4.15 – 4.11 (m, 1H, Cp), 4.11 – 4.08 (m, 1H, Cp), 4.05
– 3.91 (m, 6H, Cp’ and Cp), 3.65 – 3.54 (m, 1H, Cp), 3.37 (d, JH-
= 15.0 Hz, 1H, CHCH(CH3)2), 2.75 – 2.56 (m, 1H,
P
CHCH(CH3)2), 1.27 (d, JH-P = 7.0 Hz, 3H, CHCH(CH3)2), 1.10 (d,
JH-P = 7.0 Hz, 3H, CHCH(CH3)2); 13C{1H} NMR (126 MHz,
CDCl3) δ 134.78 (d, JC-P = 94.1 Hz, P(O)Ph2), 132.24 (d, JC-P
=
93.5 Hz, P(O)Ph2), 132.04 (d, JC-P = 8.2 Hz, P(O)Ph2), 131.17 –
130.93 (m, P(O)Ph2), 128.24 (d, JC-P = 11.2 Hz, P(O)Ph2), 127.77
(d, JC-P = 11.1 Hz, P(O)Ph2), 85.09 (s, Cp), 70.12 (s, Cp), 68.75
(d, JC-P = 4.4 Hz, Cp), 68.64 (s, Cp’), 67.34 (s, Cp’), 66.98 (s,
Cp’), 46.22 (d, JC-P = 66.6 Hz, CHCH(CH3)2), 32.13 (s,
CHCH(CH3)2), 23.00 (s, CHCH(CH3)2), 21.45 (d, JC-P = 9.8 Hz,
CHCH(CH3)2); 31P{1H} NMR (202 MHz, CDCl3) δ 32.30.
HRMS (ESI-TOF) m/z: [M]+ calcd for C26H27FeOP 442.1149;
Found: 442.1135.
Cp), 3.45 – 3.32 (m, 1H, CHCH3), 1.60 (dd, J H-P = 15.8, J H-H
=
7.2 Hz, 3H, CHCH3); 13C{1H} NMR (126 MHz, CDCl3) δ 131.94
(d, JC-P = 93.7 Hz, P(O)Ph2), 131.82 (d, JC-P = 8.6 Hz, P(O)Ph2),
131.50 (d, JC-P = 2.6 Hz, P(O)Ph2), 131.35 (d, JC-P = 2.8 Hz,
P(O)Ph2), 131.29 (d, JC-P = 8.6 Hz, P(O)Ph2), 130.48 (d, JC-P
=
4.2.5. (2,2-Dimethyl-1-ferrocenylpropyl)diphenylphosphine oxide
95.6 Hz, P(O)Ph2), 128.33 (d, JC-P = 11.2 Hz, P(O)Ph2), 127.79
(d, JC-P = 11.4 Hz, P(O)Ph2), 85.50 (s, Cp), 69.29 (d, JC-P = 1.8
Hz, Cp), 68.39 (s, Cp’), 67.53 (s, Cp), 67.38 (d, JC-P = 1.3 Hz,
Cp), 67.17 (s, Cp), 35.61 (d, JC-P = 66.4 Hz, CHCH3), 13.84 (d,
JC-P = 1.5 Hz, CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ
33.86.
(3e). orange solid, 30.4 mg (27% yield); mp217 – 218oC; Rf
1
(petroleum ether/ethyl acetate 1:2) = 0.6. H NMR (500 MHz,
CDCl3) δ 7.91 – 7.76 (m, 2H, P(O)Ph2), 7.49 – 7.32 (m, 5H,
P(O)Ph2), 7.24 – 7.17 (m, 1H, P(O)Ph2), 7.16 – 7.10 (m, 2H,
P(O)Ph2), 4.28 – 4.16 (m, 1H, Cp), 4.05 – 4.00 (m, 5H, Cp’),
3.99 – 3.96 (m, 1H, Cp), 3.82 – 3.73 (m, 1H, Cp), 3.67 – 3.57 (m,
1H, Cp), 3.04 (d, JH-P = 9.8 Hz, 1H, CHC(CH3)3), 1.33 (s, 9H,
CHC(CH3)3); 13C{1H} NMR (126 MHz, CDCl3) δ 137.30 (d, JC-P
= 88.8 Hz, P(O)Ph2), 134.54 (d, JC-P = 98.0 Hz, P(O)Ph2), 130.98
(d, JC-P = 8.3 Hz, P(O)Ph2), 130.70 (d, JC-P = 2.7 Hz, P(O)Ph2),
130.57 (d, JC-P = 8.5 Hz, P(O)Ph2), 129.96 (d, JC-P = 2.6 Hz,
4.2.2. Diphenyl(1-ferrocenylpropyl)phosphine oxide (3b). Yellow
solid, 57.4 mg (54% yield); mp 166 – 167oC; Rf (petroleum
ether/ethyl acetate 1:3) = 0.6. 1H NMR (500 MHz, CDCl3) δ 7.86
– 7.70 (m, 2H, P(O)Ph2), 7.55 – 7.36(m, 6H, P(O)Ph2), 7.34 –
7.25 (m, 2H, P(O)Ph2), 4.12 – 4.08 (m, 5H, Cp’), 4.08 – 4.03 (m,
2H, Cp), 3.94 – 3.79 (m, 1H, Cp), 3.56 – 3.38 (m, 1H, Cp), 3.22
– 3.03 (m, 1H, CHCH2CH3), 2.29 – 2.04 (m, 2H, CHCH2CH3),
1.15 (t, J H-H = 7.4 Hz, 3H, CHCH2CH3); 13C{1H} NMR (126
MHz, CDCl3) δ 132.87 (d, JC-P = 92.9 Hz, P(O)Ph2), 131.88 (d,
JC-P = 8.4 Hz, P(O)Ph2), 131.36 (d, JC-P = 2.1 Hz, P(O)Ph2),
131.28 (d, JC-P = 8.6 Hz, P(O)Ph2), 131.16 (d, JC-P = 1.8 Hz,
P(O)Ph2), 130.41 (s, P(O)Ph2), 128.19 (d, JC-P = 11.1 Hz,
P(O)Ph2), 127.67 (d, JC-P = 11.2 Hz, P(O)Ph2), 86.32 (s, Cp),
69.43 (s, Cp), 68.46 (s, Cp’), 67.93 (s, Cp), 67.49 (s, Cp), 66.81
(s, Cp), 42.48 (d, JC-P = 65.2 Hz, CHCH2CH3), 23.42 (s,
CHCH2CH3), 14.69 (d, JC-P = 4.7 Hz, CHCH2CH3); 31P{1H}
NMR (202 MHz, CDCl3) δ 33.76. HRMS (ESI-TOF) m/z: [M]+
calcd for C25H25FeOP 428.0992; Found: 428.0997.
P(O)Ph2), 128.30 (d, JC-P = 11.0 Hz, P(O)Ph2), 127.19 (d, JC-P
=
11.2 Hz, P(O)Ph2), 86.47 (s, Cp), 72.41 (d, JC-P = 3.3 Hz, Cp),
71.06 (d, JC-P = 5.7 Hz, Cp), 69.51 (s, Cp’), 67.64 (s, Cp), 65.65
(s, Cp), 47.99 (d, JC-P = 66.8 Hz, CHC(CH3)3), 35.96 (d, JC-P
=
1.3 Hz, CHC(CH3)3), 30.65 (d, JC-P = 6.3 Hz CHC(CH3)3); 31P{1H}
NMR (202 MHz, CDCl3) δ 31.64; HRMS (ESI-TOF) m/z: [M]+
calcd for C27H29FeOP 456.1305; Found: 456.1302.
4.2.6. (Ferrocenylmethyl)diphenylphosphine oxide (3f).25 Yellow
solid, 76.0 mg (76% yield); mp 198 – 199oC; Rf (petroleum
1
ether/ethanol100:1) = 0.5. H NMR (500 MHz, CDCl3) δ 7.72 –
7.61 (m, 4H, P(O)Ph2), 7.54 – 7.47 (m, 2H, P(O)Ph2), 7.47 – 7.38
(m, 4H, P(O)Ph2), 4.14 – 4.04 (m, 5H, Cp’), 4.03 – 3.95 (m, 4H,
Cp), 3.42 (d, JH-P = 12.7 Hz, 2H, CH2P(O)Ph2); 13C{1H} NMR
(126 MHz, CDCl3) δ 132.29 (d, JC-P = 97.8 Hz, P(O)Ph2), 131.67
(d, JC-P = 2.7 Hz, P(O)Ph2), 131.18 (d, JC-P = 9.2 Hz, P(O)Ph2),
128.34 (d, JC-P = 11.6 Hz, P(O)Ph2), 77.67 (d, JC-P = 2.6 Hz, Cp),
69.75 (d, JC-P = 2.2 Hz, Cp), 68.81 (s, Cp’), 67.94 (s, Cp), 33.28
(d, JC-P = 67.4 Hz, CH2P(O)Ph2); 31P{1H} NMR (202 MHz,
CDCl3) δ 28.71.
4.2.3. Diphenyl(1-ferrocenylbutyl)phosphine oxide (3c). Yellow
solid, 78.3 mg (71% yield); mp 161-162oC; Rf (petroleum
ether/ethyl acetate 1:2) = 0.6. 1H NMR (500 MHz, CDCl3) δ 7.81
– 7.71 (m, 2H, P(O)Ph2), 7.54 – 7.36 (m, 6H, P(O)Ph2), 7.35 –
7.28 (m, 2H, P(O)Ph2), 4.10 – 4.07 (m, 5H, Cp’), 4.07 – 4.04 (m,
2H, Cp), 3.91 – 3.84 (m, 1H, Cp), 3.49 – 3.42 (m, 1H, Cp), 3.26
– 3.16 (m, 1H, CHCH2CH2CH3), 2.21 – 1.92 (m, 2H,
CHCH2CH2CH3), 1.70 – 1.46 (m, 2H, CHCH2CH2CH3), 0.92 (t,
JH-H = 7.3 Hz, 3H, CHCH2CH2CH3); 13C{1H} NMR (126 MHz,
4.2.7. Bis(3,5-dimethylphenyl)(1-ferrocenylethyl)phosphine oxide
(3g). Yellow solid, 107.4 mg (91% yield); mp 181 – 182oC; Rf
1
(petroleum ether/ethyl acetate 1:2) = 0.6. H NMR (500 MHz,
CDCl3) δ 132.84 (d, JC-P = 93.2 Hz, P(O)Ph2), 131.93 (d, JC-P
=
CDCl3) δ 7.44 – 7.30 (m, 2H, P(O)Ph2), 7.20 – 6.99 (m, 4H,
P(O)Ph2), 4.22 – 4.40 (m, 7H, Cp’ and Cp), 3.93 (m, 1H, Cp),
3.52 (m, 1H, Cp), 3.39 – 3.22 (m, 1H, CHCH3), 2.35 (s, 6H, Ph-
CH3), 2.25 (s, 6H, Ph- CH3), 1.57 (dd, JH-P = 15.2, JH-H = 6.2 Hz,
8.3 Hz, P(O)Ph2), 131.40 (d, JC-P = 2.0 Hz, P(O)Ph2), 131.30 (d,
JC-P = 8.6 Hz, P(O)Ph2), 131.19 (d, JC-P = 2.0 Hz, P(O)Ph2),
130.76 (d, JC-P = 95.8 Hz, P(O)Ph2), 128.20 (d, JC-P = 11.2 Hz,
P(O)Ph2), 127.69 (d, JC-P = 11.2 Hz, P(O)Ph2), 86.54 (s, Cp),

6
Tetrahedron
3H, CHCH3); 13C{1H} NMR (126 MHz, CDCl3) δ 137.90 (d, JC-P
92.9 Hz, P(O)Ph2), 129.55 (d, JC-P = 8.3 Hz, P(O)Ph2), 128.65 (d,
JC-P = 8.6 Hz, P(O)Ph2), 85.16 (s, Cp), 70.43 (d, JC-P = 1.9 Hz,
Cp), 68.77 (d, JC-P = 5.1 Hz, Cp), 68.59 (s, Cp’), 67.12 (s, Cp),
66.80 (s, Cp), 45.77 (d, JC-P = 66.6 Hz, CHCH(CH3)2), 31.79 (s,
CHCH(CH3)2), 22.54 (s, CHCH(CH3)2), 21.77 (d, JC-P = 10.3 Hz,
CHCH(CH3)2), 21.30 (s, Ph- CH3), 21.15 (s, Ph-CH3); 31P{1H}
NMR (202 MHz, CDCl3) δ 33.02; HRMS (ESI-TOF) m/z: [M]+
calcd for C30H35FeOP 498.1775; Found: 498.1759.
A
CCEPTED MANUSCRIPT
= 11.7 Hz, P(O)Ph2), 137.29 (d, JC-P = 12.0 Hz, P(O)Ph2), 133.15
(d, JC-P = 1.9 Hz, P(O)Ph2), 132.95 (d, JC-P = 2.2 Hz, P(O)Ph2),
131.69 (d, JC-P = 92.8 Hz, P(O)Ph2), 130.40 (d, JC-P = 95.2 Hz,
P(O)Ph2), 129.37 (d, JC-P = 8.6 Hz, P(O)Ph2), 128.85 (d, JC-P
=
8.5 Hz, P(O)Ph2), 85.93 (s, Cp), 69.79 (s, Cp), 69.48 (s, Cp),
68.37 (s, Cp’), 67.50 (s, Cp), 67.00 (s, Cp), 35.38 (d, JC-P = 65.9
Hz, CHCH3), 21.26 (s, Ph-CH3), 21.12 (s, Ph-CH3), 13.93 (s,
CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ 34.39; HRMS
(ESI-TOF) m/z: [M]+ calcd for C28H31FeOP 470.1462; Found:
470.1460.
4.2.11. (2,2-Dimethyl-1-ferrocenylpropyl)bis(3,5-dimethylphenyl)
phosphine oxide (3k). Yellow oil, 75.8 mg (59% yield); mp 213 –
214oC; Rf (petroleum ether/ethyl acetate 1:2) = 0.6. H NMR
1
4.2.8.
Bis(3,5-dimethylphenyl)(1-ferrocenylpropyl)phosphine
(500 MHz, CDCl3) δ 7.46 – 7.36 (m, 2H, P(O)Ph2), 7.07 – 7.00
(m, 1H, P(O)Ph2), 6.98 – 6.89 (m, 2H, P(O)Ph2), 6.84 – 6.77 (m,
1H, P(O)Ph2), 4.24 – 4.15 (m, 1H, Cp), 4.07 – 4.00 (m, 5H, Cp’),
4.00 – 3.95 (m, 1H, Cp), 3.82 – 3.74 (m, 1H, Cp), 3.66 – 3.57 (m,
1H, Cp), 2.98 (d, J H-P = 10.0 Hz, 1H, CHC(CH3)3), 2.32 (s, 6H,
Ph-CH3), 2.16 (s, 6H, Ph-CH3), 1.33 (s, 9H, CHC(CH3)3); 13C{1H}
NMR (126 MHz, CDCl3) δ 137.73 (d, JC-P = 11.6 Hz, P(O)Ph2),
136.95 (d, JC-P = 88.4 Hz, P(O)Ph2), 136.43 (d, JC-P = 11.7 Hz,
P(O)Ph2), 134.00 (d, JC-P = 97.0 Hz, P(O)Ph2), 132.37 (s,
P(O)Ph2), 131.53 (s, P(O)Ph2), 128.68 (d, JC-P = 8.2 Hz, P(O)Ph2),
oxide (3h). Yellow solid, 71.5 mg (59% yield); mp 134 – 135oC;
Rf (petroleum ether/ethyl acetate 1:2) = 0.6. 1H NMR (500 MHz,
CDCl3) δ 7.42 – 7.32 (m, 2H, P(O)Ph2), 7.15 – 6.98 (m, 4H,
P(O)Ph2), 4.14 – 4.02 (m, 7H, Cp’ and Cp), 3.90 (m, 1H, Cp),
3.50 (m, 1H, Cp), 3.16 – 2.99 (m, 1H, CHCH2CH3), 2.34 (s, 6H,
Ph-CH3), 2.24 (s, 6H, Ph-CH3), 2.22 – 2.05 (m, 2H, CHCH2CH3),
1.14 (t, J H-H = 7.2 Hz, 3H, CHCH2CH3); 13C{1H} NMR (126
MHz, CDCl3) δ 137.71 (d, JC-P = 11.8 Hz, P(O)Ph2), 137.12 (d,
JC-P = 11.9 Hz, P(O)Ph2), 133.03 (d, JC-P = 2.2 Hz, P(O)Ph2),
132.79 (d, JC-P = 2.4 Hz, P(O)Ph2), 132.04 (s, P(O)Ph2), 130.40
(d, JC-P = 94.8 Hz, P(O)Ph2), 129.49 (d, JC-P = 8.5 Hz, P(O)Ph2),
128.91 (d, JC-P = 8.6 Hz, P(O)Ph2), 86.55 (s, Cp), 69.60 (s, Cp),
68.40 (s, Cp’), 68.00 (s, Cp), 67.37 (s, Cp), 66.64 (s, Cp), 42.24
(d, JC-P = 64.9 Hz, CHCH2CH3), 23.35 (s, CHCH2CH3), 21.23 (s,
Ph-CH3), 21.08 (s, 6H, Ph-CH3), 14.77 (d, JC-P = 5.0 Hz,
CHCH2CH3); 31P{1H} NMR (202 MHz, CDCl3) δ 34.67; HRMS
(ESI-TOF) m/z: [M]+ calcd for C29H33FeOP 484.1618; Found:
484.1613.
128.16 (d, JC-P = 8.4 Hz, P(O)Ph2), 86.64 (s, Cp), 72.41 (d, JC-P
=
2.5 Hz, Cp), 71.08 (d, J = 5.4 Hz, Cp), 69.38 (s, Cp’), 67.31 (s,
Cp), 65.34 (s, Cp), 48.00 (d, JC-P = 66.1 Hz, CHC(CH3)3), 35.85
(s, CHC(CH3)3), 30.70 (d, JC-P = 6.0 Hz, CHC(CH3)3), 21.30 (s,
Ph-CH3), 21.15 (s, Ph-CH3); 31P{1H} NMR (202 MHz, CDCl3) δ
32.44; HRMS (ESI-TOF) m/z: [M]+ calcd for C31H37FeOP
512.1931; Found: 512.1919.
4.2.12. Ethyl phenyl(1-ferrocenylethyl)phosphinate (3l). brown
oil, 79.9 mg (84% yield); Rf (petroleum ether/ethyl acetate 1:2) =
0.6. 1H NMR (500 MHz, CDCl3) δ 7.67 – 7.17 (m, 5H, Ph), 4.27
– 3.98 (m, 9H, Cp’ and Cp), 3.98 – 3.71 (m, 2H, OCH2CH3), 3.17
– 2.76 (m, 1H, CHCH3), 1.65 – 1.37 (m, 3H, CHCH3), 1.32 –
1.21 (m, 3H, OCH2CH3); 13C{1H} NMR (126 MHz, CDCl3) δ
132.61 (d, JC-P = 9.0 Hz, Ph), 132.27 (d, JC-P = 9.1 Hz, Ph),
131.79 (d, JC-P = 2.5 Hz, Ph), 129.24 (d, JC-P = 121.0 Hz, Ph),
127.87 (d, JC-P = 12.0 Hz, Ph), 127.74 (d, JC-P = 12.2 Hz, Ph),
85.54 (s, Cp), 85.42 (s, Cp), 69.69 (s, Cp), 69.35 (s, Cp), 68.30
(m, Cp’), 67.45 (s, Cp), 67.29 (d, JC-P = 1.5 Hz, Cp), 67.06 (s,
Cp), 66.64 (s, Cp), 66.51 (s, Cp), 60.64 (d, JC-P = 6.8 Hz,
OCH2CH3), 35.40 (m, CHCH3), 35.27 (d, JC-P = 95.3 Hz), 16.33
(d, JC-P = 6.2 Hz, OCH2CH3), 13.61 (s, CHCH3), 13.05 (s,
CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ 43.47, 42.98;
HRMS (ESI-TOF) m/z: [M]+ calcd for C20H23FeO2P 382.0785;
Found: 382.0781.
4.2.9. Bis(3,5-dimethylphenyl)(1-ferrocenylbutyl)phosphine oxide
(3i). Yellow oil, 97.8 mg (79% yield); mp156 – 157oC; Rf
1
(petroleum ether/ethyl acetate 1:2) = 0.6. H NMR (500 MHz,
CDCl3) δ 7.39 – 7.32 (m, 2H, P(O)Ph2), 7.13 – 6.99 (m, 4H,
P(O)Ph2), 4.10 – 4.06 (m, 7H, Cp’ and Cp), 3.94 – 3.83 (m, 1H,
Cp), 3.52
– 3.44 (m, 1H, Cp), 3.21 – 3.08 (m, 1H,
CHCH2CH2CH3), 2.33 (s, 6H, Ph-CH3), 2.23 (s, 6H, Ph-CH3),
2.17 – 1.92 (m, 2H, CHCH2CH2CH3), 1.69 – 1.44 (m, 2H,
CHCH2CH2CH3), 0.92 (t, J H-H = 7.3 Hz, 3H, CHCH2CH2CH3);
13C{1H} NMR (126 MHz, CDCl3) δ 137.70 (d, JC-P = 11.8 Hz,
P(O)Ph2), 137.13 (d, JC-P = 11.9 Hz, P(O)Ph2), 133.02 (d, JC-P
=
2.5 Hz, P(O)Ph2), 132.78 (d, JC-P = 2.5 Hz, P(O)Ph2), 132.53 (d,
JC-P = 92.4 Hz, P(O)Ph2), 130.56 (d, JC-P = 94.7 Hz, P(O)Ph2),
129.52 (d, JC-P = 8.5 Hz, P(O)Ph2), 128.90 (d, JC-P = 8.6 Hz,
P(O)Ph2), 86.86 (s, Cp), 69.62 (s, Cp), 68.42 (s, Cp’), 68.04 (s,
Cp), 67.39 (s, Cp), 66.63 (s, Cp), 40.53 (d, JC-P = 64.9 Hz,
CHCH2CH2CH3), 32.23 (s, CHCH2CH2CH3), 22.92 (d, JC-P = 4.9
Hz, CHCH2CH2CH3), 21.24 (s, Ph-CH3), 21.09 (s, Ph-CH3),
14.43 (s, CHCH2CH2CH3); 31P{1H} NMR (202 MHz, CDCl3) δ
34.48; HRMS (ESI-TOF) m/z: [M]+ calcd for C30H35FeOP
498.1775; Found: 498.1770.
4.2.13. Ethyl phenyl(1-ferrocenylpropyl)phosphinate (3m).
brown oil, 44.4 mg (45% yield); Rf (petroleum ether/ethyl
acetate 1:2) = 0.6. 1H NMR (500 MHz, CDCl3) δ 7.62 – 7.28 (m,
5H, Ph), 4.61 – 3.40 (overlapped signals, m, 11H, Cp’, Cp,
OCH2CH3), 2.85 – 2.60 (m, 1H, CHCH2CH3), 2.30 – 1.81 (m, 2H,
CHCH2CH3), 1.47
– 1.05 (overlapped signals, m, 6H,
4.2.10. Bis (3,5-dimethylphenyl)(2-methyl-1-ferrocenylpropyl)
CHCH2CH3, OCH2CH3); 13C{1H} NMR (126 MHz, CDCl3) δ
132.75 (d, JC-P = 9.1 Hz, Ph), 132.38 (d, JC-P = 9.1 Hz, Ph),
131.77 (s, Ph), 130.55 (s, Ph), 129.59 (s, Ph), 128.57 (s, Ph),
127.90 (d, JC-P = 12.0 Hz, Ph), 127.75 (d, JC-P = 12.0 Hz, Ph),
86.39 (s, Cp), 86.23 (s, Cp), 70.00 (d, JC-P = 1.5 Hz, Cp), 69.65 (d,
JC-P = 1.7 Hz, Cp), 69.26 (s, Cp), 68.45 (d, JC-P = 1.4 Hz, Cp’),
67.44 (s, Cp), 67.31 (d, JC-P = 2.1 Hz, Cp), 67.25 (s, Cp), 67.08 (s,
Cp), 67.02 (s, Cp), 60.65 (d, JC-P = 6.9 Hz, OCH2CH3), 60.53 (d,
JC-P = 6.9 Hz, OCH2CH3), 42.67 (d, JC-P = 93.3 Hz, CHCH2CH3),
42.25 (d, JC-P = 93.3 Hz, CHCH2CH3), 23.39 (s, CHCH2CH3),
22.83 (s, CHCH2CH3), 16.40 (d, JC-P = 6.3 Hz, OCH2CH3), 14.33
(d, JC-P = 3.3 Hz, CHCH2CH3), 14.25 (d, JC-P = 4.2 Hz,
CHCH2CH3); 31P{1H} NMR (202 MHz, CDCl3) δ 43.75, 43.26;
phosphine oxide (3j). Yellow oil, 99.6 mg (80% yield); mp 169-
1
170oC; Rf (petroleum ether/ethyl acetate 1:2) = 0.6. H NMR
(500 MHz, CDCl3) δ 7.40 – 7.29 (m, 2H, P(O)Ph2), 7.23 – 7.13
(m, 2H, P(O)Ph2), 7.13 – 7.06 (m, 1H, P(O)Ph2), 7.06 – 6.99 (m,
1H, P(O)Ph2), 4.14 (m, 1H, Cp), 4.11 (m, 1H, Cp), 4.01 – 3.97
(m, 1H, Cp), 3.97 – 3.92 (m, 5H, Cp’), 3.72 (m, 1H, Cp), 3.39 –
3.24 (m, 1H, CHCH(CH3)2), 2.70 – 2.51 (m, 1H, CHCH(CH3)2),
2.33 (s, 6H, Ph-CH3), 2.26 (s, 6H, Ph- CH3), 1.21 (d, J H-H = 7.0
Hz, 3H, CHCH(CH3)2), 1.10 (d,
J
= 7.0 Hz, 3H,
H-H
CHCH(CH3)2); 13C{1H} NMR (126 MHz, CDCl3) δ 137.77 (d,
JC-P = 11.8 Hz, P(O)Ph2), 137.23 (d, JC-P = 11.8 Hz, P(O)Ph2),
134.54 (d, JC-P = 93.4 Hz, P(O)Ph2), 132.80 (d, JC-P = 2.6 Hz,
P(O)Ph2), 132.67 (d, JC-P = 2.7 Hz, P(O)Ph2), 132.34 (d, JC-P
=

7
HRMS (ESI-TOF) m/z: [M]+ calcd for C21H2 FeO2P 396.0942;
Found: 396.0924.
CHC(CH3)3), 30.35 (s, CHC(CH3)3), 16.29 (m, OCH2CH3);
5
ACCEPTED MANUSCRIPT
31P{1H} NMR (202 MHz, CDCl3) δ 43.21, 42.89; HRMS (ESI-
TOF) m/z: [M]+ calcd for C23H29FeO2P 424.1255; Found:
424.1256.
4.2.14. Ethyl phenyl(1-ferrocenylbutyl)phosphinate (3n). brown
oil, 74.4 mg (73% yield); Rf (petroleum ether/ethyl acetate 1:2) =
0.6. 1H NMR (500 MHz, CDCl3) δ 7.55 – 7.23 (m, 5H, Ph), 4.18
– 3.68 (m, 11H, overlapped signals, m, 11H, Cp’, Cp, OCH2CH3),
2.95 – 2.64 (m, 1H, CHCH2CH2CH3), 2.05 – 1.87 (m, 2H,
CHCH2CH2CH3), 1.81 – 1.20 (m, 2H, CHCH2CH2CH3), 1.33 –
1.21 (m, 3H, OCH2CH3), 1.09 – 0.88 (m, 3H, CHCH2CH2CH3);
13C{1H} NMR (126 MHz, CDCl3) δ 132.68 (d, JC-P = 9.0 Hz, Ph),
132.31 (d, JC-P = 9.1 Hz, Ph), 131.71 (d, JC-P = 2.4 Hz, Ph),
130.00 (d, JC-P = 120.1 Hz, Ph), 128.99 (d, JC-P = 120.1 Hz, Ph),
127.85 (d, JC-P = 12.0 Hz, Ph), 127.70 (d, JC-P = 12.0 Hz, Ph),
86.46 (s, Cp), 86.35 (s, Cp), 69.95 (d, JC-P = 1.9 Hz, Cp), 69.62 (d,
4.2.17. Ethyl (ferrocenyl(phenyl)methyl) (phenyl)phosphinate
(3q). Yellow solid, 69.9 mg (63% yield); mp 188-189oC; Rf
1
(petroleum ether/ethyl acetate 1:2) = 0.6. H NMR (500 MHz,
CDCl3) δ 7.64 – 7.04 (m, 10H, Ph), 4.33 – 3.71 (m, 11H, Cp’ and
Cp overlapped with OCH2CH3), 1.23 and 1.10 (two triplet, JH-H
=
7.0 Hz, 3H, OCH2CH3); 13C{1H} NMR (126 MHz, CDCl3) δ
137.02 (d, JC-P = 5.5 Hz, Ph), 136.71 (d, JC-P = 2.6 Hz, Ph),
132.30 (d, JC-P = 9.2 Hz, Ph), 131.99 (d, JC-P = 9.2 Hz, Ph),
131.83 (d, JC-P = 2.6 Hz, Ph), 131.65 (d, JC-P = 2.6 Hz, Ph),
130.77 (d, JC-P = 4.7 Hz, Ph), 130.03 (s, Ph), 129.98 (s, Ph),
129.92 (s, Ph), 129.78 (d, JC-P = 4.9 Hz, Ph), 128.02 (d, JC-P = 1.1
Hz, Ph), 127.88 (s, Ph), 127.82 (s, Ph), 127.78 (s, Ph), 127.72 (s,
Ph), 127.03 (d, JC-P = 2.0 Hz, Ph), 126.90 (d, JC-P = 2.3 Hz, Ph),
84.36 (d, JC-P = 3.7 Hz, Cp), 84.15 (s, Cp), 70.18 (d, JC-P = 2.4 Hz,
Cp), 69.99 (d, JC-P = 2.3 Hz, Cp), 69.52 (s, Cp), 68.44 (s, Cp’),
68.37 (s, Cp’), 68.25 (s, Cp), 68.21 (s, Cp), 68.03 (s, Cp), 67.08
(s, Cp), 61.15 (s, OCH2CH3), 61.09 (s, OCH2CH3), 61.03 (s,
OCH2CH3), 50.04 (d, JC-P = 13.9 Hz, CHPh), 49.31 (d, JC-P = 14.1
JC-P = 1.6 Hz, Cp), 69.24 (s, Cp), 68.41 (s, Cp’), 67.43 (d, JC-P
=
1.7 Hz, Cp), 67.39 (s, Cp), 67.27 (d, JC-P = 2.1 Hz, Cp), 67.21 (s,
Cp), 67.02 (s, Cp), 66.96 (s, Cp), 60.61 (d, JC-P = 7.0 Hz,
OCH2CH3), 60.48 (d, JC-P = 7.0 Hz, OCH2CH3), 40.64 (d, JC-P
93.2 Hz, CHCH2CH2CH3), 40.17 (d, JC-P 93.9 Hz,
=
=
CHCH2CH2CH3), 32.22 (s, CHCH2CH2CH3), 31.61 (s,
CHCH2CH2CH3), 22.39 (d, JC-P = 4.1 Hz, CHCH2CH2CH3),
16.35 (d, JC-P = 6.2 Hz, OCH2CH3), 14.40 (d, JC-P = 11.0 Hz,
CHCH2CH2CH3); 31P{1H} NMR (202 MHz, CDCl3) δ 43.75,
43.23; HRMS (ESI-TOF) m/z: [M]+ calcd for C22H27FeO2P
410.1098; Found: 410.1085.
Hz, CHPh), 16.39 (d, JC-P = 6.3 Hz, OCH2CH3), 16.27 (d, JC-P
=
6.0 Hz, OCH2CH3); 31P{1H} NMR (202 MHz, CDCl3) δ 38.50,
38.22; HRMS (ESI-TOF) m/z: [M]+ calcd for C25H25FeO2P
444.0942; Found: 444.0947.
4.2.15. Ethyl (2-methyl-1-ferrocenylpropyl)(phenyl)phosphinate
(3o). brown oil, 50.0 mg (49% yield); Rf (petroleum ether/ethyl
acetate 1:2) = 0.6. 1H NMR (500 MHz, CDCl3) δ 7.72 – 7.62 (m,
1H, Ph), 7.55 – 7.38 (m, 3H, Ph), 7.34 – 7.27 (m, 1H, Ph), 4.33 –
3.92 (m, 10H, Cp’ and Cp overlapped with OCH2CH3), 3.87 –
3.57 (m, 1H, OCH2CH3), 3.07 – 2.80 (m, 1H, CHCH(CH3)2),
2.77 – 2.18 (m, 1H, CHCH(CH3)2), 1.37 – 0.86 (m, 9H,
CHCH(CH3)2 and OCH2CH3); 13C{1H} NMR (126 MHz, CDCl3)
δ 132.92 (d, JC-P = 9.3 Hz, Ph), 132.31 (d, JC-P = 9.2 Hz, Ph),
131.74 (d, JC-P = 2.6 Hz, Ph), 131.59 (d, JC-P = 2.6 Hz, Ph),
130.98 (d, JC-P = 90.1 Hz, Ph), 128.18 (d, JC-P = 12.0 Hz, Ph),
127.76 (d, JC-P = 11.9 Hz, Ph), 86.02 (s, Cp), 84.10 (s, Cp), 70.76
(s, Cp), 70.32 (s, Cp), 68.87 (s, Cp’), 68.61 (s, Cp’), 67.88 (d, JC-P
= 3.9 Hz, Cp), 67.47 (s, Cp), 67.10 (s, Cp), 67.07 (s, Cp), 66.94
(s, Cp), 60.39 (d, JC-P = 6.7 Hz, OCH2CH3), 59.99 (d, JC-P = 6.8
Hz, OCH2CH3), 46.68 (d, JC-P = 94.3 Hz, CHCH(CH3)2), 46.11 (d,
JC-P = 96.7 Hz, CHCH(CH3)2), 31.57 (s, CHCH(CH3)2), 30.60 (s,
CHCH(CH3)2), 23.60 (s, CHCH(CH3)2), 21.82 (d, JC-P = 12.2 Hz,
CHCH(CH3)2), 20.97 (overlapped signals, m, CHCH(CH3)2),
16.35 (d, JC-P = 6.7 Hz, OCH2CH3); 31P{1H} NMR (202 MHz,
CDCl3) δ 43.78, 41.60; HRMS (ESI-TOF) m/z: [M]+ calcd for
C22H27FeO2P 410.1098; Found: 410.1097.
4.2.18. Diethyl (1-ferrocenylethyl)phosphonate (3r). brown oil,
59.9 mg (69% yield); Rf (petroleum ether/ethyl acetate 1:2) = 0.6.
1H NMR (500 MHz, CDCl3) δ 4.38 – 4.26 (m, 1H, Cp), 4.26 –
4.04 (m, 8H, Cp’, Cp), 4.01 – 3.84 (m, 4H, OCH2CH3), 2.99 –
2.81 (m, 1H, CHCH3), 1.58 (dd, JH-P = 17.8, JH-H = 7.0 Hz, 3H,
CHCH3), 1.22 (m, 6H, OCH2CH3); 13C{1H} NMR (126 MHz,
CDCl3) δ 85.67 (d, JC-P = 1.3 Hz, Cp), 69.32 (d, JC-P = 2.2 Hz,
Cp), 68.48 (s, Cp’), 67.61 (s, Cp), 67.38 (s, Cp), 66.46 (d, JC-P
2.1 Hz, Cp), 61.98 (d, JC-P = 7.0 Hz, OCHCH3), 32.34 (d, JC-P
=
=
136.9 Hz, CHCH3), 16.38 (d, JC-P = 5.7 Hz, OCH2CH3), 14.23 (d,
JC-P = 4.5 Hz, CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ
28.36; HRMS (ESI-TOF) m/z: [M]+ calcd for C16H23FeO3P
350.0734; Found: 350.0738.
4.2.19. Diethyl (1-ferrocenylpropyl)phosphonate (3s). brown oil,
44.1 mg (49% yield); Rf (petroleum ether/ethyl acetate 1:2) = 0.6.
1H NMR (500 MHz, CDCl3) δ 4.32 – 4.23 (m, 1H, Cp), 4.22 –
4.05 (m, 8H, Cp, Cp’), 4.01 – 3.75 (m, 4H, OCH2CH3), 2.72 –
2.56 (m, 1H, CHCH2CH3), 2.26 – 1.95 (m, 2H, CHCH2CH3),
1.31 – 1.15 (overlapped signals, m, 9H, CHCH2CH3, OCH2CH3);
13C{1H} NMR (126 MHz, CDCl3) δ 86.22 (d, JC-P = 1.7 Hz, Cp),
69.35 (d, JC-P = 2.3 Hz, Cp), 68.47 (s, Cp’), 67.36 (s, Cp), 67.12
(s, Cp), 67.09 (s, Cp), 61.92 (d, JC-P = 7.1 Hz, OCH2CH3), 61.52
(d, JC-P = 7.2 Hz, OCH2CH3), 39.35 (d, JC-P = 134.3 Hz,
CHCH2CH3), 23.73 (d, JC-P = 3.4 Hz, CHCH2CH3), 16.29 (d, JC-P
= 6.0 Hz, OCH2CH3), 13.80 (d, JC-P = 3.8 Hz, CHCH2CH3);
31P{1H} NMR (202 MHz, CDCl3) δ 28.97; HRMS (ESI-TOF)
m/z: [M]+ calcd for C17H25FeO3P 364.0891; Found: 364.0883.
4.2.16.
Ethyl
(2,2-dimethyl-1-ferrocenylpropyl)
(phenyl)
phosphinate (3p). brown oil, 59.8 mg (56% yield); Rf (petroleum
ether/ethyl acetate 1:2) = 0.6. 1H NMR (500 MHz, CDCl3) δ 7.79
– 7.64 (m, 1H, Ph), 7.52 – 7.32 (m, 3H, Ph), 7.30 – 7.21 (m, 1H,
Ph), 4.19 – 3.84 (m, 9H, Cp’ and Cp overlapped with OCH2CH3),
3.84 – 3.53 (m, 1H, OCH2CH3), 2.90 – 2.63 (m, 1H, CHC(CH3)3),
1.40 – 0.98 (m, 12H, CHC(CH3)3 and OCH2CH3); 13C{1H} NMR
(126 MHz, CDCl3) δ134.39 (d, JC-P = 118.9 Hz, Ph), 132.25 (d,
JC-P = 121.5 Hz, Ph), 132.11 (s, Ph), 132.04 (s, Ph), 131.96 (s,
Ph), 131.34 (d, JC-P = 2.6 Hz, Ph), 131.04 (d, JC-P = 2.6 Hz, Ph),
128.05 (d, JC-P = 12.1 Hz, Ph), 127.50 (d, JC-P = 12.0 Hz, Ph),
85.14 (d, JC-P = 4.2 Hz, Cp), 84.88 (d, JC-P = 1.9 Hz, Cp), 71.76 (d,
4.2.20. (1- Ferrocenylethyl)di-p-tolylphosphine oxide (3t).
Yellow solid, 103.6 mg (94% yield); mp 56 – 57oC; Rf
1
(petroleum ether/ethyl acetate 1:2) = 0.6. H NMR (500 MHz,
CDCl3) δ 7.68 – 7.58 (m, 2H, Ph), 7.43 – 7.33 (m, 2H, Ph), 7.26
– 7.21 (m, 2H, Ph), 7.16 – 7.08 (m, 2H, Ph), 4.15 – 4.03 (m, 7H,
Cp’, Cp), 3.95 – 3.88 (m, 1H, Cp), 3.57 – 3.48 (m, 1H, Cp), 3.41
– 3.30 (m, 1H, CHCH3), 2.37 (s, 3H, Ph-CH3), 2.32 (s, 3H, Ph-
CH3), 1.58 (dd, JH-P = 15.8, JH-H = 7.3 Hz, 3H, CHCH3); 13C{1H}
NMR (126 MHz, CDCl3) δ 141.69 (d, JC-P = 2.7 Hz, Ph), 141.54
(d, JC-P = 2.7 Hz, Ph), 131.81 (d, JC-P = 8.9 Hz, Ph), 131.23 (d, JC-
JC-P = 2.7 Hz, Cp), 71.42 (d, JC-P = 2.7 Hz, Cp), 70.74 (d, JC-P
=
7.5 Hz, Cp), 70.03 (d, JC-P = 9.3 Hz, Cp), 69.30 (s, Cp’), 69.25 (s,
Cp’), 67.26 (s, Cp), 66.68 (s, Cp), 66.37 (s, Cp), 66.26 (s, Cp),
60.17 (d, JC-P = 6.7 Hz, OCH2CH3), 59.96 (d, J = 7.1 Hz,
OCH2CH3), 49.83 (d, JC-P = 122.4 Hz, CHC(CH3)3), 49.06 (d, JC-P
= 122.5 Hz, CHC(CH3)3), 35.24 (s, CHC(CH3)3), 35.11 (s,
= 8.9 Hz, Ph), 128.96 (d, JC-P = 11.5 Hz, Ph), 128.83 (d, JC-P
=
P

8
Tetrahedron
ACCEPTED MANUSCRIPT
96.4 Hz, Ph), 128.46 (d, JC-P = 11.7 Hz, Ph), 127.17 (d, JC-P
97.9 Hz, Ph), 85.68 (s, Cp), 69.32 (s, Cp), 68.30 (s, Cp’), 67.35 (s,
Cp), 67.10 (s, Cp), 35.63 (d, JC-P = 66.7 Hz, CHCH3), 21.39 (d,
JC-P = 3.9 Hz, Ph-CH3), 13.79 (s, CHCH3); 31P{1H} NMR (202
MHz, CDCl3) δ 34.25; HRMS (ESI-TOF) m/z: [M]+ calcd for
C26H27FeOP 442.1149; Found: 442.1130.
=
0.36 mmol H-phosphorus oxide or ethyl phenylphosphinate,
0.15 mmol 1,1’-ferrocenyl diketone-derived N-tosylhydrazone,
0.03 mmol of CuI and 0.90 mmol K2CO3 were charged into 25
mL oven dried flask, and backfilled with argon three times. 5
mL freshly distilled 1,4 dioxane was then injected into the
flask, then heated to reflux for 18 h. The crude reaction mixture
was allowed to reach room temperature, the solvent was
eliminated under vacuum. Ammonia water and dichloromethane
was added and the layers were separated. The aqueous phase was
extracted three times with dichloromethane. The combined
organic phase was dried over Na2SO4. The concentrated residue
was purified by column chromatography over silica gel using
petroleum ether/ dichloromethane/ NEt3 (1:2:0.1) as eluent to get
the product 5.
4.2.21. Bis(4-fluorophenyl)(1- ferrocenylethyl)phosphine oxide
(3u). Yellow solid, 70.1mg (62% yield); mp 203 – 204oC; Rf
1
(petroleum ether/ethyl acetate 1:2) = 0.6. H NMR (500 MHz,
CDCl3) δ 7.79 – 7.69 (m, 2H, Ph), 7.52 – 7.40 (m, 2H, Ph), 7.19
– 7.15 (m, 2H, Ph), 7.10 – 6.97 (m, 2H, Ph), 4.16 – 4.05 (m, 7H,
Cp’, Cp), 3.42 – 3.35 (m, 1H, Cp), 3.55 – 3.44 (m, 1H, Cp), 3.42
– 3.25 (m, 1H, CHCH3), 1.59 (dd, J H-P = 16.1, JH-H = 7.2 Hz, 3H,
CHCH3); 13C{1H} NMR (126 MHz, CDCl3) δ 164.87 (d, JC-P
=
253.3 Hz, Ph), 134.50 (s, Ph), 134.43 (s, Ph), 134.36 (s, Ph),
134.29 (s, Ph), 133.85 (s, Ph), 133.77 (s, Ph), 133.70 (s, Ph),
128.13 (d, JC-P = 3.3 Hz, Ph), 127.36 (d, JC-P = 3.3 Hz, Ph),
126.40 (d, JC-P = 3.5 Hz, Ph), 125.62 (d, JC-P = 2.1 Hz, Ph),
116.08 (dd, JC-P = 21.5, 13.4 Hz, Ph), 115.86 (dd, JC-P = 21.2,
12.3 Hz, Ph), 115.30 (dd, JC-P = 21.2, 12.5 Hz, Ph), 85.25 (s, Cp),
69.31 (d, JC-P = 1.5 Hz, Cp), 68.53 (s, Cp’), 67.74 (s, Cp), 67.42
(s, Cp), 67.37 (s, Cp), 36.01 (d, JC-P = 67.5 Hz, CHCH3), 13.84 (d,
JC-P = 1.2 Hz, CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ
32.95; 19F NMR (470 MHz, CDCl3) δ -106.85, -107.15; HRMS
(ESI-TOF) m/z: [M]+ calcd for C24H21F2FeOP 450.0648; Found:
450.0669.
4.3.1.
1,1'-Bis((1-diphenylphosphinyl)ethyl)-ferrocene
(5a).
Yellow solid, 62.7 mg (65% yield); mp 178 – 179oC; Rf
(petroleum ether/dichloromethane / triethylamine1:3:0.1) = 0.6.
1H NMR (500 MHz, CDCl3) δ 7.86 – 7.67 (m, 4H, Ph), 7.67 –
7.40 (m, 12H, Ph), 7.40 – 7.29 (m, 4H, Ph), 4.15 – 4.07 (m, 1H,
Cp), 4.07 – 3.97 (m, 3H, Cp), 3.94 – 3.84 (m, 2H, Cp), 3.51 –
3.39 (m, 2H, Cp), 3.39 – 3.19 (m, 2H, CHCH3), 1.67 – 1.42 (m,
6H, CHCH3); 13C{1H} NMR (126 MHz, CDCl3) δ 131.84 (d, JC-P
= 15.9 Hz, Ph), 131.49 (d, JC-P = 8.6 Hz, Ph), 131.39 (d, JC-P
=
2.5 Hz, Ph), 131.23 (s, Ph), 131.16 (s, Ph), 131.06 (s, Ph),
131.00 (s, Ph), 130.94 (s, Ph), 130.50 (d, JC-P = 4.4 Hz, Ph),
129.74 (d, JC-P = 4.4 Hz, Ph), 127.63 (d, JC-P = 11.4 Hz, Ph),
85.52 (s, Cp), 85.39 (s, Cp), 69.81 (d, JC-P = 1.5 Hz, Cp), 69.55 (d,
JC-P = 1.5 Hz, Cp), 68.25 (s, Cp), 68.06 (s, Cp), 68.02 (s, Cp),
67.69 (s, Cp), 67.64 (s, Cp), 67.31 (s, Cp), 66.70 (s, Cp), 35.26 (d,
JC-P = 66.2 Hz, CHCH3), 35.08 (d, JC-P = 66.3 Hz, CHCH3), 13.73
(d, JC-P = 1.4 Hz, CHCH3), 13.67 (d, JC-P = 1.3 Hz, CHCH3);
31P{1H} NMR (202 MHz, CDCl3) δ 33.45, 33.37; HRMS (ESI-
TOF) m/z: [M]+ calcd for C38H36FeO2P2 642.1540; Found:
642.1535.
4.2.22. Bis(4-methoxyphenyl)(1- ferrocenylethyl)phosphine oxide
(3v). Yellow solid, 95.9mg (81% yield); mp 44 – 45oC; Rf
1
(petroleum ether/ethyl acetate 1:2) = 0.6. H NMR (500 MHz,
CDCl3) δ 7.74 – 7.54 (m, 2H, Ph), 7.46 – 7.32 (m, 2H, Ph), 7.07
– 6.89 (m, 2H, Ph), 6.89 – 6.75 (m, 2H, Ph), 4.19 – 3.99 (m, 7H,
Cp, Cp’), 3.99 – 3.89 (m, 1H, Cp), 3.83 (s, 3H, OCH3), 3.79 (s,
3H, OCH3), 3.59 – 3.48 (m, 1H, Cp), 3.41 – 3.27 (m, 1H,
CHCH3), 1.58 – 1.56 (m, 3H, CHCH3); 13C{1H} NMR (126 MHz,
CDCl3) δ 161.99 (d, JC-P = 2.0 Hz, Ph), 161.93 (d, JC-P = 2.1 Hz,
Ph), 133.72 (d, JC-P = 9.6 Hz, Ph), 133.06 (d, JC-P = 9.9 Hz, Ph),
123.40 (d, JC-P = 100.2 Hz, Ph), 121.42 (d, JC-P = 102.0 Hz, Ph),
113.79 (d, JC-P = 12.1 Hz, Ph), 113.29 (d, JC-P = 12.2 Hz, Ph),
85.82 (s, Cp), 69.37 (s, Cp), 68.36 (s, Cp’), 67.34 (s, Cp), 67.20
(s, Cp), 55.12 (d, JC-P = 8.5 Hz OCH3), 36.00 (d, JC-P = 67.6 Hz,
CHCH3), 13.78 (s, CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ
34.24; HRMS (ESI-TOF) m/z: [M]+ calcd for C26H27FeO3P
474.1047; Found: 474.1042.
4.3.2. 1-((1-Diphenylphosphinyl)ethyl)-1'-(1-((4-methylphenyl)
sulfonyl)ethyl)-ferrocene (6a). Yellow solid, 27.7 mg (31% yield);
mp 65
–
66oC; Rf (petroleum ether/ dichloromethane/
1
triethylamine 1:3:0.1) = 0.5. H NMR (500 MHz, CDCl3) δ 7.80
– 7.68 (m, 2H, Ph), 7.57 – 7.50 (m, 1H, Ph), 7.50 – 7.40 (m, 5H,
Ph), 7.38 – 7.29 (m, 4H, Ph), 7.20 – 7.15 (m, 2H, Ph), 4.16 –
3.78 (m, 8H, Cp), 3.44 – 3.39 (m, 1H, CH(CH3)S(O)2Ph-CH3),
3.36 – 3.24 (m, 1H, CH(CH3)P(O)Ph2), 2.43 – 3.32 (s, 3H, Ph-
CH3), 1.67 – 1.58 (m, 3H, CH(CH3)S(O)2Ph-CH3), 1.58 – 1.47
(m, 3H, CH(CH3)P(O)Ph2); 13C{1H} NMR (126 MHz, CDCl3) δ
143.95 (s, Ph), 132.67 – 132.31 (m, Ph), 131.68 – 130.99 (m, Ph),
130.96 – 130.26 (m, Ph), 129.22 – 128.87 (m, Ph), 128.88 –
128.45 (m, Ph), 128.27 – 127.85 (m, Ph), 127.67 – 127.30 (m,
Ph), 85.98 (d, JC-P = 7.5 Hz, Cp), 80.96 (d, JC-P = 14.9 Hz, Cp),
71.00 (s, Cp), 70.75 (s, Cp), 69.89 (s, Cp), 69.57 (s, Cp), 69.24 (s,
Cp), 69.01 – 68.63 (m, Cp), 68.34 – 67.27 (m, Cp), 66.92 (s, Cp),
66.65 (s, Cp), 61.65 (d, JC-P = 10.6 Hz, CH(CH3)S(O)2Ph-CH3),
4.2.23. Bis(2,6-dimethylphenyl)(1- ferrocenylethyl)phosphine
oxide (3w). Yellow solid, 22.8mg (19% yield); mp 188 – 189oC;
Rf (petroleum ether/ethyl acetate 1:2) = 0.6. 1H NMR (500 MHz,
CDCl3) δ 7.22 – 7.14 (m, 1H, Ph), 7.09 – 6.94 (m, 3H, Ph), 6.81
– 6.71 (m, 2H, Ph), 4.40 – 4.31 (m, 1H, Cp), 4.16 – 4.07 (m, 5H,
Cp’), 4.05 – 3.97 (m, 1H, Cp), 3.75 – 3.67 (m, 1H, Cp), 3.66 –
3.54 (m, 1H, CHCH3), 3.43 – 3.35 (m, 1H, Cp), 2.52 (s, 6H, Ph-
CH3), 2.19 (s, 6H, Ph-CH3), 1.89 (dd, JH-P = 14.8, JH-H = 6.8 Hz,
3H, CHCH3); 13C{1H} NMR (126 MHz, CDCl3) δ 135.05 (d, JC-P
= 81.4 Hz, Ph), 131.56 (d, JC-P = 89.5 Hz, Ph), 130.36 (s, Ph),
35.25
–
34.29
(m,
CH(CH3)P(O)Ph2),
21.15
(s,
CH(CH3)S(O)2Ph-CH3), 13.64 (s, CH(CH3)S(O)2Ph-CH3), 13.59
(d, JC-P = 1.3 Hz, CH(CH3)P(O)Ph2); 31P{1H} NMR (202 MHz,
CDCl3) δ 33.30, 33.22; HRMS (ESI-TOF) m/z: [M]+ calcd for
C33H33FeO3PS 596.1237; Found: 596.1241.
130.28 (s, Ph), 130.12 (d, JC-P = 2.6 Hz, Ph), 129.45 (d, JC-P
=
10.6 Hz, Ph), 87.04 (s, Cp), 69.17 (d, JC-P = 2.1 Hz, Cp), 68.34 (s,
Cp’), 68.10 (d, JC-P = 1.5 Hz, Cp), 67.30 (s, Cp), 66.71 (s, Cp),
38.08 (d, JC-P = 59.8 Hz, CHCH3), 22.86 (d, J = 3.3 Hz, Ph-CH3),
22.52 (d, J = 3.9 Hz, Ph-CH3), 15.57 (d, JC-P = 2.1 Hz, CHCH3);
31P{1H} NMR (202 MHz, CDCl3) δ 43.22; HRMS (ESI-TOF)
m/z: [M]+ calcd for C28H31FeOP 470.1462; Found: 470.1460.
4.3.3. 1,1'-Bis((1-diphenylphosphinyl)propyl)-ferrocene (5b).
Yellow solid, 53.9 mg (54% yield); mp 191 – 192oC; Rf
1
(petroleum ether/ethyl acetate 1:2) = 0.6. H NMR (500 MHz,
CDCl3) δ 7.80 – 7.67 (m, 4H, Ph), 7.56 – 7.36 (m, 12H, Ph), 7.35
– 7.27 (m, 4H, Ph), 4.06 – 3.92 (m, 4H, Cp), 3.88 – 3.75 (m, 2H,
Cp), 3.40 – 3.29 (m, 2H, Cp), 3.16 – 2.98 (m, 2H, CHCH2CH3),
2.23 – 1.94 (m, 4H, CHCH2CH3), 1.15 – 1.02 (m, 6H,
CHCH2CH3); 13C{1H} NMR (126 MHz, CDCl3) δ 133.18 (d, JC-P
= 6.6 Hz, Ph), 132.44 (d, JC-P = 6.9 Hz, Ph), 131.99 (d, JC-P = 2.4
4.3. General Procedure for Cu-catalyzed Reaction of 1,1’-
Ferrocenyl Diketone-derived N-tosylhydrazones with H-
phosphorus Oxides and Ethyl Phenylphosphinate:

9
Hz, Ph), 131.92 (d, JC-P = 2.5 Hz, Ph), 131.52 (d, JC-P = 2.6 Hz,
Ph), 131.40 – 131.23 (m, Ph), 130.96 (d, JC-P = 4.9 Hz, Ph),
130.20 (d, JC-P = 5.0 Hz, Ph), 128.35 (d, JC-P = 3.2 Hz, Ph),
128.26 (d, JC-P = 3.2 Hz, Ph), 127.81 (s, Ph), 127.72 (s, Ph),
86.78 (s, Cp), 86.56 (s, Cp), 70.24 (s, Cp), 70.14 (s, Cp), 68.73 (s,
Cp), 68.58 (s, Cp), 68.37 (s, Cp), 68.08 (s, Cp), 67.74 (s, Cp),
42.59 (d, JC-P = 65.0 Hz, CHCH2CH3), 42.35 (d, JC-P = 65.0 Hz,
CHCH2CH3), 23.51 (d, JC-P = 19.2 Hz, CHCH2CH3), 14.80 (d, JC-
69.81 (d, JC-P = 1.9 Hz, Cp), 68.75 (s, Cp), 68.54 (s, Cp), 68.51
ACCEPTED MANUSCRIPT
(s, Cp), 68.17 (s, Cp), 67.88 (d, JC-P = 1.2 Hz, Cp), 67.60 (d, JC-P
= 1.3 Hz, Cp), 35.85 (d, JC-P = 67.2 Hz, CHCH3), 35.63 (d, JC-P
=
67.4 Hz, CHCH3), 13.98 (d, JC-P = 1.4 Hz, CHCH3), 13.92 (d, JC-P
= 1.5 Hz, CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ 32.95,
32.86; HRMS (ESI-TOF) m/z: [M]+ calcd for C38H32F4FeO2P2
714.1163; Found: 714.1154.
4.3.7.
1,1'-Bis((1-(bis(4-methoxy)phosphinyl))ethyl)-ferrocene
= 4.7 Hz, CHCH2CH3), 14.75 (d, JC-P = 4.7 Hz, CHCH2CH3);
(5f). Yellow solid, 75.5 mg (66% yield); mp 49 – 50oC; Rf
(petroleum ether/ dichloromethane / triethylamine 1:3:0.1) = 0.6.
1H NMR (500 MHz, CDCl3) δ 7.65 – 7.56 (m, 4H, Ph), 7.40 –
7.30 (m, 4H, Ph), 6.98 – 6.90 (m, 4H, Ph), 6.87 – 6.79 (m, 4H,
Ph), 4.05 – 3.95 (m, 4H, Cp), 3.93 – 3.87 (m, 2H, Cp), 3.84 (s,
6H, OCH3), 3.80 (s, 6H, OCH3), 3.50 – 3.40 (m, 2H, Cp), 3.31 –
3.19 (m, 2H, CHCH3), 1.55 – 1.45 (m, 6H, CHCH3); 13C{1H}
NMR (126 MHz, CDCl3) δ 162.10 (d, JC-P = 2.8 Hz, ), 162.04 (s),
δ 162.14 – 162.00 (m, Ph), 134.90 – 132.05 (m, Ph), 125.39 –
119.12 (m, Ph), 114.61 – 112.52 (m, Ph), 86.16 (s, Cp), 86.01 (s,
Cp), 70.27 (s, Cp), 69.95 (s, Cp), 68.41 (s, Cp), 68.32 (s, Cp),
68.10 (s, Cp), 68.00 (s, Cp), 67.95 (s, Cp), 67.55 (s, Cp), 55.24 (s,
OCH3), 55.17 (s, OCH3), 36.62 – 35.16 (m, CHCH3), 13.95 (d,
P
31P{1H} NMR (202 MHz, CDCl3) δ 33.85, 33.79; HRMS (ESI-
TOF) m/z: [M+Na]+ calcd for C40H40FeNaO2P2 693.1751; Found:
693.1739.
4.3.4.
1,1'-Bis((1-diphenylphosphinyl)butyl)-ferrocene
(5c).
Yellow solid, 43.7 mg (42% yield); mp185 – 186oC; Rf
1
(petroleum ether/ethyl acetate 1:2) = 0.6. H NMR (500 MHz,
CDCl3) δ 7.82 – 7.65 (m, 4H, Ph), 7.57 – 7.36 (m, 12H, Ph), 7.36
– 7.22 (m, 4H, Ph), 4.05 – 3.91 (m, 4H, Cp), 3.87 – 3.75 (m, 2H,
Cp), 3.40
CHCH2CH2CH3), 2.25 – 1.78 (m, 4H, CHCH2CH2CH3), 1.67 –
1.37 (m, 4H, CHCH2CH2CH3), 0.98 0.78 (m, 6H,
CHCH2CH2CH3); 13C{1H} NMR (126 MHz, CDCl3) δ 132.77 (d,
C-P = 93.3 Hz, Ph), 131.97 (d, JC-P = 4.3 Hz, Ph), 131.90 (d, JC-P
– 3.27 (m, 2H, Cp), 3.21 – 3.06 (m, 2H,
–
J
J
C-P = 1.3 Hz, CHCH3), 13.89 (d, JC-P = 1.3 Hz, CHCH3); 31P{1H}
= 4.3 Hz, Ph), 131.52 (s, Ph), 131.39 – 131.19 (m, Ph), 131.06 (d,
JC-P = 14.5 Hz, Ph), 130.30 (d, JC-P = 14.1 Hz, Ph), 128.29 (d, JC-P
NMR (202 MHz, CDCl3) δ 34.34, 34.25; HRMS (ESI-TOF) m/z:
[M]+ calcd for C42H44FeO6P2 762.1963; Found: 762.1955.
= 10.2 Hz, Ph), 127.82 (d, JC-P = 2.5 Hz, Ph), 127.73 (d, JC-P
=
4.3.8.
1,1'-Bis((1-(bis(4-methylphenyl)phosphinyl))ethyl)-
2.5 Hz, Ph), 87.01 (s, Cp), 86.77 (s, Cp), 70.28 (s, Cp), 70.23 (s,
Cp), 68.71 (s, Cp), 68.50 (s, Cp), 68.35 (s, Cp), 68.06 (s, Cp),
67.67 (s, Cp), 40.92 (d, JC-P = 65.0 Hz, CHCH2CH2CH3), 40.67
(d, JC-P = 65.1 Hz, CHCH2CH2CH3), 32.41 (d, JC-P = 25.0 Hz,
CHCH2CH2CH3), 22.99 (s, CHCH2CH2CH3), 14.54 (d, JC-P = 4.7
Hz, CHCH2CH2CH3); 31P{1H} NMR (202 MHz, CDCl3) δ 33.76,
33.73; HRMS (ESI-TOF) m/z: [M+Na]+ calcd for
C42H44FeNaO2P2 721.2064; Found: 721.2051.
ferrocene (5g). Yellow solid, 57.6 mg (55% yield); mp 139 –
140oC; Rf (petroleum ether/ dichloromethane / triethylamine
1:3:0.1) = 0.6. 1H NMR (500 MHz, CDCl3) δ 7.64 – 7.53(m, 4H,
Ph), 7.38 – 7.30 (m, 4H, Ph), 7.27 – 7.21 (m, 4H, Ph), 7.17 –
7.08 (m, 4H, Ph), 4.08 – 4.03 (m, 1H, Cp), 4.03 – 3.97 (m, 3H,
Cp), 3.91 – 3.85 (m, 2H, Cp), 3.49 – 3.46 (m, 1H, Cp), 3.46 –
3.42 (m, 1H, Cp), 3.33 – 3.24 (m, 2H, CHCH3), 2.40 – 2.36 (m,
6H, Ph-CH3), 2.35 – 2.31 (m, 6H, Ph-CH3), 1.56 – 1.47 (m, 6H,
4.3.5. 1,1'-Bis(1-diphenylphosphinyl-2-methylpropyl)-ferrocene
CHCH3); 13C{1H} NMR (126 MHz, CDCl3) δ 141.97 (d, JC-P
=
(5d). Yellow solid, 27.8 mg (27% yield); mp 169 – 170oC; Rf
2.6 Hz, Ph), 141.81 (d, JC-P = 1.4 Hz, Ph), 131.98 (d, JC-P = 8.7
Hz, Ph), 131.55 – 131.24 (m, Ph), 129.33 (s, Ph), 129.24 –
129.04 (m, Ph), 128.67 (d, JC-P = 11.7 Hz, Ph), 128.56 (s, Ph),
128.42 (s, Ph), 127.58 (s, Ph), 127.52 (s, Ph), 126.81 (s, Ph),
126.74 (s, Ph), 86.10 (s, Cp), 85.96 (s, Cp), 70.30 (s, Cp), 70.00
(s, Cp), 68.43 (s, Cp), 68.39 (s, Cp), 68.20 (s, Cp), 68.01 (s, Cp),
1
(petroleum ether/ethyl acetate 1:2) = 0.6. H NMR (500 MHz,
CDCl3) δ 7.79 – 7.62 (m, 4H, Ph), 7.62 – 7.38 (m, 12H, Ph), 7.38
– 7.27 (m, 4H, Ph), 4.04 – 3.21 (m, 10H, Cp overlapped with
CHCH2CH3), 2.76 – 2.44 (m, 2H, CHCH(CH3)2), 1.32 – 1.19 (m,
6H, CHCH(CH3)2), 1.17 – 0.98 (m, 6H, CHCH(CH3)2); 13C{1H}
NMR (126 MHz, CDCl3) δ 135.16 (d, JC-P = 3.5 Hz, Ph), 134.41
(d, JC-P = 3.9 Hz, Ph), 132.37 – 132.06 (m, Ph), 131.28 (s, Ph),
131.17 (s, Ph), 131.10 (s, Ph), 128.47 – 128.23 (m, Ph), 127.92 –
127.62 (m, Ph), 86.12 (s, Cp), 85.60 (s, Cp), 71.10 (d, JC-P = 1.8
Hz, Cp), 70.97 (d, JC-P = 1.7 Hz, Cp), 69.33 (d, JC-P = 3.9 Hz, Cp),
69.26 (d, JC-P = 3.6 Hz, Cp), 68.64 (s, Cp), 68.50 (s, Cp), 68.30 (s,
Cp), 67.92 (s, Cp), 46.76 (s, CHCH(CH3)2), 46.24 (s,
CHCH(CH3)2), 32.72 (s, CHCH(CH3)2), 32.34 (s, CHCH(CH3)2),
23.75 (s, CHCH(CH3)2), 23.40 (s, CHCH(CH3)2), 21.36 – 21.14
(m, CHCH(CH3)2); 31P{1H} NMR (202 MHz, CDCl3) δ 32.31,
32.18; HRMS (ESI-TOF) m/z: [M]+ calcd for C42H44FeO2P2
698.2166; Found: 698.2161.
67.66 (s, Cp), 35.78 (d, JC-P = 66.5 Hz, CHCH3), 35.62 (d, JC-P
=
66.6 Hz, CHCH3), 21.56 (d, JC-P = 3.9 Hz, Ph-CH3), 14.03 (d, JC-P
= 5.6 Hz, CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ 34.32,
34.23; HRMS (ESI-TOF) m/z: [M]+ calcd for C42H44FeO2P2
698.2166; Found: 698.2159.
4.3.9. 1,1'-Bis((1-(ethoxyphenylphosphinyl))ethyl)-ferrocene (5h).
Yellow oil, 17.2 mg (27% yield); Rf (petroleum ether/
dichloromethane / triethylamine 1:3:0.1) = 0.6. H NMR (500
1
MHz, CDCl3) δ 7.54 – 7.29 (m, 10H, Ph), 4.07 – 3.57 (m, 12H,
overlapped signals, Cp, OCH2CH3), 3.16 – 2.78 (m, 2H, CHCH3),
1.48 – 1.42 (m, 6H, CHCH3), 1.30 – 1.22 (m, 6H, OCH2CH3);
13C{1H} NMR (126 MHz, CDCl3) δ 132.69 (d, JC-P = 9.3 Hz, Ph),
132.37 (d, JC-P = 9.1 Hz, Ph), 132.00 – 131.81 (m, Ph), 129.21 (d,
JC-P = 120.6 Hz, Ph), 128.22 – 127.45 (m, Ph), 85.90 – 85.58 (m,
Cp), 70.66 (s, Cp), 70.27 (s, Cp), 69.96 (s, Cp), 68.71 – 67.72 (m,
Cp), 67.35 – 66.35 (m, Cp), 60.85 – 60.70 (m, Cp), 36.14 – 34.58
(m, CHCH3), 16.41 (d, JC-P = 6.3 Hz, OCH2CH3), 14.05 – 12.63
(m, CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ 43.41, 43.37,
43.31, 43.00, 42.96, 42.89, 42.85; HRMS (ESI-TOF) m/z: [M]+
calcd for C30H36FeO4P2 578.1438; Found: 578.1433.
4.3.6. 1,1'-Bis ((1-(bis (4-fluorophenyl) phosphinyl)) ethyl)-
ferrocene (5e). Yellow solid, 63.5 mg (59% yield); mp 180 –
181oC; Rf (petroleum ether/ dichloromethane / triethylamine
1:3:0.1) = 0.6. 1H NMR (500 MHz, CDCl3) δ 7.79 – 7.62 (m, 4H,
Ph), 7.50 – 7.36 (m, 4H, Ph), 7.22 – 7.09 (m, 4H, Ph), 7.08 –
6.69 (m, 4H, Ph), 4.12 – 3.96 (m, 4H, Cp), 3.95 – 3.88 (m, 2H,
Cp), 3.48 – 3.39 (m, 2H, Cp), 3.34 – 3.19 (m, 2H, CHCH3), 1.58
– 1.45 (m, 6H, CHCH3); 13C{1H} NMR (126 MHz, CDCl3) δ
164.91 (dd, JC-F = 253.7, JC-P = 3.2 Hz), 134.35 – 134.10 (m, Ph),
133.87 – 133.52 (m, Ph), 128.04 – 127.52 (m, Ph), 127.25 –
126.78 (m, Ph), 126.49 – 126.14 (m, Ph), 125.66 – 125.35 (m,
Ph), 116.11 – 115.74 (m, Ph), 115.38 (dd, JC-F = 21.2, JC-P = 12.5
Hz, Ph), 85.68 (s, Cp), 85.56 (s, Cp), 70.04 (d, JC-P = 1.7 Hz, Cp),
4.3.10. 1,1'-Bis((1-(bis(3,5-dimethylphenyl)phosphinyl))ethyl)-
ferrocene (5i). Yellow solid, 30.1 mg (27% yield); mp 225 –
226oC; Rf (petroleum ether/ dichloromethane / triethylamine
1:3:0.1) = 0.6. 1H NMR (500 MHz, CDCl3) δ 7.37 – 7.29 (m, 4H,

10
Tetrahedron
ACCEPTED MANUSCRIPT
Ph), 7.16 – 7.10 (m, 2H, Ph), 7.08 – 7.00 (m, 6H, Ph), 4.12 –
13C{1H} NMR (126 MHz, CDCl3) δ 139.43 (d, JC-P = 9.7 Hz, Ph),
137.35 – 136.70 (m, Ph), 134.49 – 133.30 (m, Ph), 128.99 –
127.70 (m, Ph), 92.21 (d, JC-P = 14.9 Hz, Cp), 75.78 (d, JC-P = 6.0
Hz, Cp), 73.83 – 72.79 (m, Cp), 71.58 – 71.08 (m, Cp), 70.47 (s,
Cp), 69.72 (s, Cp), 68.47 (s, Cp), 68.20 (s, Cp), 67.18 (s, Cp),
32.12 (d, JC-P = 11.3 Hz, CHCH3), 17.88 (d, JC-P = 19.0 Hz,
CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ 6.55, 5.94, -15.93,
-16.37.
4.07 (m, 1H, Cp), 4.07 – 4.01 (m, 3H, Cp), 3.94 – 3.87 (m, 2H,
Cp), 3.50 – 3.41 (m, 2H, Cp), 3.35 – 3.21 (m, 2H, Cp), 2.35 –
2.31 (m, 12H, Ph-CH3), 2.26 – 2.21 (m, 12H, Ph-CH3), 1.57 –
1.47 (m, 6H, CHCH3); 13C{1H} NMR (126 MHz, CDCl3) δ
138.17 – 137.78 (m, Ph), 137.37 (d, JC-P = 11.9 Hz, Ph), 133.25
(d, JC-P = 2.6 Hz, Ph), 133.05 (d, JC-P = 2.6 Hz, Ph), 132.21 –
129.62 (m, Ph), 129.44 (d, JC-P = 8.6 Hz, Ph), 129.07 – 128.56 (m,
Ph), 86.12 (s, Cp), 85.99 (s, Cp), 70.29 (s, Cp), 69.94 (s, Cp),
68.39 – 67.40 (m, Cp), 36.06 – 34.32 (m, CHCH3), 21.22 (d, JC-P
= 17.9 Hz, Ph-CH3), 13.98 (d, JC-P = 6.0 Hz, CHCH3); 31P{1H}
NMR (202 MHz, CDCl3) δ 34.46, 34.41; HRMS (ESI-TOF) m/z:
[M+H]+ calcd for C46H53FeO2P2 755.2870; Found: 755.2865.
4.5.2. 1-(Dicyclohexylphosphino)-2-(1-(diphenylphosphino) ethyl)
-ferrocene (8b). Yellow solid, 208.1mg (14% yield); mp 132 –
136oC; Rf (petroleum ether/ ethyl acetate 100:1) = 0.4. H NMR
1
(500 MHz, CDCl3) δ 7.39 – 7.20 (m, 10H, Ph), 4.19 – 4.16 (m,
1H, Cp), 4.16 – 4.12 (m, 6H, Cp), 3.85 – 3.79 (m, 1H, Cp), 3.64
– 3.54 (m, 1H, CHCH3), 2.28 – 1.10 (m, 25H, CHCH3 and Cy);
13C{1H} NMR (126 MHz, CDCl3) δ 138.72 (d, JC-P = 19.0 Hz,
Ph), 135.97 (d, JC-P = 21.3 Hz, Ph), 132.01 (d, JC-P = 15.2 Hz, Ph),
129.24 (s, Ph), 128.24 (d, JC-P = 4.4 Hz, Ph), 127.92 (d, JC-P = 7.6
Hz, Ph), 127.44 (s, Ph), 77.91 (d, JC-P = 1.9 Hz, Cp), 71.05 (s,
4.4. Synthesis of diphenyl (1-ferrocenylethyl) phosphine 7:
A 0.7mL portion (4.8mmol, 20equiv.) of Et3N and 0.5mL
(4.8mmol, 20equiv.) of SiHCl3 were added to a toluene solution
of 100mg (0.24mmol) of 3a. The suspension was heated to reflux
overnight under an inert atmosphere. After the mixture was
cooled to room temperature, 5mL of a NaOH solution in
degassed water (30%) was added and the mixture was stirred at
60oC for 2h. The two phases were separated under an inert
atmosphere, the water phase was extracted twice with dry Et2O.
The organic phase was dried with MgSO4 and filtered, and the
solvent was evaporated under vacuum. The obtained orange oil
was purified by aluminium oxide column chromatography
(petroleum ether) to afford desired product 7.
Cp), 70.09 (d, JC-P = 1.9 Hz, Cp), 69.43 (s, Cp), 68.58 (dd, JC-P
=
8.8, 3.4 Hz, Cp), 67.82 (s, Cp), 34.8 – 19.5 (m, Cy, CHCH3,
CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ 4.66, 4.63, -13.39.
4.6. Synthesis of 1,1'-bis((1-diphenylphosphino)ethyl)-ferrocene
9:
A 0.9mL portion (6.2mmol, 40equiv.) of Et3N and 0.6mL
(6.2mmol, 40equiv.) of SiHCl3 were added to a toluene solution
of 100mg (0.155mmol) of 3a. The suspension was heated to
reflux overnight under an inert atmosphere. After the mixture
was cooled to room temperature, 5mL of a NaOH solution in
degassed water (30%) was added and the mixture was stirred at
60oC for 2h. The two phases were separated under an inert
atmosphere, and the water phase was extracted twice with dry
Et2O. The organic phase was dried with MgSO4 and filtered, and
the solvent was evaporated under vacuum. The obtained orange
oil was purified by aluminium oxide column chromatography
(petroleum ether) to afford desired product 9.
4.4.1. Diphenyl(1-ferrocenylethyl)phosphine (7).26 Yellow solid,
0.99g (96% yield); mp 79 – 80oC; Rf (petroleum ether) = 0.5. H
1
NMR (500 MHz, CDCl3) δ 7.54 – 7.48 (m, 2H, Ph), 7.38 – 7.30
(m, 3H, Ph), 7.27 – 7.13 (m, 5H, Ph), 4.15 – 4.05 (m, 5H, Cp’),
4.04 – 4.00 (m, 1H, Cp), 4.00 – 4.35 (m, 1H, Cp), 3.90 – 3.85 (m,
1H, Cp), 3.51 – 3.37 (m, 1H, Cp), 3.34 – 3.17 (m, 1H, CHCH3),
1.47 (dd, J H-P = 14.7, JH-H = 7.1 Hz 3H, CHCH3); 13C{1H} NMR
(126 MHz, CDCl3) δ 137.09 (d, JC-P = 14.7 Hz, Ph), 136.96 (d,
JC-P = 16.1 Hz, Ph), 134.03 (d, JC-P = 19.2 Hz, Ph), 133.91 (d, JC-P
= 16.7 Hz, Ph), 133.49 (d, JC-P = 19.2 Hz, Ph), 128.61 (d, JC-P
=
4.6.1. 1,1'-Bis((1-diphenylphosphino)ethyl)-ferrocene (9). Yellow
15.5 Hz, Ph), 128.45 (d, JC-P = 10.2 Hz, Ph), 128.25 (d, JC-P = 6.7
Hz, Ph), 127.73 (d, JC-P = 7.1 Hz, Ph), 91.27 (d, JC-P = 14.8 Hz,
Cp), 68.75 (d, JC-P = 2.7 Hz, Cp), 68.26 (s, Cp’), 67.01 (s, Cp),
66.65 (s, Cp), 66.30 (d, JC-P = 3.4 Hz, Cp), 32.23 (d, JC-P = 13.9
Hz, CHCH3), 17.88 (d, JC-P = 19.0 Hz, CHCH3); 31P{1H} NMR
(202 MHz, CDCl3) δ 5.61.
solid, 78.8mg(83% yield); mp 41 – 42oC; Rf (petroleum ether/
1
ethyl acetate 10:1) = 0.4. H NMR (500 MHz, CDCl3) δ 7.54 –
7.43 (m, 4H, Ph), 7.40 – 7.29 (m, 6H, Ph), 7.28 – 7.14 (m, 10H,
Ph), 4.01 – 3.81 (m, 6H, Ph), 3.43 – 3.35 (m, 2H, Ph), 3.30 –
3.12 (m, 2H, CHCH3), 1.41 (dd, J H-P = 14.7, JH-H = 7.0 Hz, 6H,
CHCH3); 13C{1H} NMR (126 MHz, CDCl3) δ 137.32 – 136.74
(m, Ph), 134.23 – 133.83 (m, Ph), 133.71 – 133.22 (m, Ph),
128.72 – 128.49 (m, Ph), 128.25 (d, JC-P = 6.6 Hz, Ph), 127.83 –
127.64 (m, Ph), 91.93 – 90.08 (m, Cp), 69.37 (d, JC-P = 2.8 Hz,
Cp), 69.13 (d, JC-P = 2.9 Hz, Cp), 67.69 (d, JC-P = 17.7 Hz, Cp),
67.38 (d, JC-P = 33.5 Hz, Cp), 66.68 (d, JC-P = 3.4 Hz, Cp), 66.32
4.5. Synthesis of 1-(diphenylphosphino)-2-(1-
(diphenylphosphino) ethyl)-ferrocene 8:
A 1.3 M t-BuLi in pentane solution (2.3mL, 3.0mmol,
o
1.2equiv.) was added at -78 C over 30 min through a syringe
pump to a solution of 7 (1g, 2.5mmol, 1equiv.) in THF (20mL).
After stirring the solution at room temperature for 1h, the
solution was cooled again to -78oC and chlorodiphenylphosphine
was added dropwise with a syringe. The reaction was warmed to
room temperature overnight. The mixture was then quenched by
the addition of saturated NaHCO3 solution (10mL). The organic
layer was separated and dried over MgSO4 and the solvent was
removed under reduced pressure, after which the filtrate was
concentrated. The residue was purified by aluminium oxide
chromatography (petroleum ether/ethyl acetate 20:1) to afford 8.
(d, JC-P = 3.4 Hz, Cp), 32.72 – 31.68 (m, CHCH3), 17.86 (d, JC-P
=
18.9 Hz, CHCH3); 31P{1H} NMR (202 MHz, CDCl3) δ 5.73, 5.68;
HRMS (ESI-TOF) m/z: [M]+ calcd for C38H36FeP2 610.1642;
Found: 610.1627.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant No. 21364005), Grassland Talent
Innovative Teams of Inner Mongolia Autonomous Region and
the project was supported by Open Research Fund of State Key
Laboratory of Polymer Physics and Chemistry, Changchun
Institute of Applied Chemistry, Chinese Academy of Sciences.
4.5.1.
1-(Diphenylphosphino)-2-(1-(diphenylphosphino)ethyl)-
ferrocene (8a). Yellow solid, 291.2mg (20% yield); mp 39 –
1
46oC; Rf (petroleum ether/ ethyl acetate 20:1) = 0.4. H NMR
Supplementary data
(500 MHz, CDCl3) δ 7.40 – 7.27 (m, 20H, Ph), 4.36 – 4.30 (m,
2H, Cp), 4.07 – 4.03 (m, 2H, Cp), 3.92 – 3.89 (m, 1H, Cp), 3.89
– 3.85 (m, 1H, Cp), 3.80 – 3.77 (m, 1H, Cp), 3.41 – 3.37 (m, 1H,
Cp), 3.09 – 3.01 (m, 1H, CHCH3), 1.51 – 1.40 (m, 3H, CHCH3);
Supplementary data (The crystal structure of compound 3u and
3w has been deposited at the Cambridge Crystallographic Data
Centre (http://www.ccdc.cam.ac.uk/) with deposition number

11
CCDC 1509037 and 1509038) associated with this article can be
found in the online version, at http://xx.
Xia, Y.; Hu, F. D.; Liu, Z. X.; Qu, P. Y.; Ge, R.; Ma, C.;
Zhang, Y.; Wang, J. B. Org. Lett. 2013, 15, 1784-1787.
ACCEPTED MANUSCRIPT
12 (a) Tréguier, B.; Hamze, A.; Provot, O.; Brion, J. -D.; Alami,
M. Tetrahedron Lett. 2009, 50, 6549-6552. (b) Barluenga, J.;
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Catal. 2009, 351, 2747-2763.
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26 Englert, U.; Ganter, B.; Kaser, M.; Klinkhammer, E.;
Wagner, T.; Salzer, A. Chem. Eur. J. 1996, 2, 523-528.