Unexpected acid-catalyzed ferrocenylmethylation of diverse nucleophiles with vinyloxymethylferrocene

Article abstract of DOI:10.1016/j.tet.2016.06.012

A new efficient approach for the ferrocenylmethylation of various alcohols, OH-, SH- and SeH-acids (carboxylic, thio- and selenophosphinic) as well as 1H-triazoles is elaborated based on the acid-catalyzed reaction with available vinyloxymethylferrocene.

Full text of DOI:10.1016/j.tet.2016.06.012

Accepted Manuscript
Unexpected acid-catalyzed ferrocenylmethylation of diverse nucleophiles with
vinyloxymethylferrocene
Ludmila A. Oparina, Alexander V. Artem'ev, Oksana V. Vysotskaya, Olga A.
Tarasova, Vladimir A. Shagun, Irina Yu. Bagryanskaya, Boris A. Trofimov
PII:
S0040-4020(16)30525-7
10.1016/j.tet.2016.06.012
TET 27826
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 24 April 2016
Revised Date: 23 May 2016
Accepted Date: 3 June 2016
Please cite this article as: Oparina LA, Artem'ev AV, Vysotskaya OV, Tarasova OA, Shagun VA,
Bagryanskaya IY, Trofimov BA, Unexpected acid-catalyzed ferrocenylmethylation of diverse
nucleophiles with vinyloxymethylferrocene, Tetrahedron (2016), doi: 10.1016/j.tet.2016.06.012.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Unexpected acid-catalyzed ferrocenylmethylation
of diverse nucleophiles with vinyloxymethylferrocene
Leave this area blank for abstract info.
L. A. Oparina, A. V. Artem’ev, O. V. Vysotskaya, O. A. Tarasova, V. A. Shagun, I. Yu. Bagryanskaya, B. A. Trofimov

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Unexpected acid-catalyzed ferrocenylmethylation of diverse nucleophiles with
vinyloxymethylferrocene
Ludmila A. Oparina,a Alexander V. Artem’ev,a Oksana V. Vysotskaya,a Olga A. Tarasova,a Vladimir A.
Shagun,a Irina Yu. Bagryanskaya,b,c Boris A. Trofimova
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation
b
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 Lavrentiev Ave., 630090, Novosibirsk,
Russian Federation
c Novosibirsk State University, 2 Pirogova Str., Novosibirsk, 630090, Russian Federation
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A new efficient approach for the ferrocenylmethylation of various alcohols, OH-, SH- and
SeH-acids (carboxylic, thio- and selenophosphinic) as well as 1H-triazoles is elaborated
based on the acid-catalyzed reaction with available vinyloxymethylferrocene. The reaction
readily occurs under mild conditions to afford product of O-, N-, S- and Se-
ferrocenylmethylation of the corresponding nucleophiles in good to high yields.
Available online
Keywords:
Electrophilic Addition
Enol Ethers
2009 Elsevier Ltd. All rights reserved
.
Ferrocene
Regioselectivity
Nucleophiles
exceptions21), that impose some restrictions on the substrate
scope. In recent years, much attention has been paid to
nucleophilic substitution of the OH group in hydroxymethyl
ferrocene using various metal-based catalysts. For instance,
1. Introduction
Ferrocene derivatives have attracted ever-growing attention
over the last few decades because of their numerous valuable
characteristics.1 A plethora of ferrocenes nowadays finds a wide
application in medicine,2 materials science,3 catalysis,3,4
organometallic5 and polymer chemistry,6 molecular recognition7
and organic synthesis.1,3,4
cerium
ammonium
nitrate
was
exploited
for
ferrocenylmethylation of diverse N-, O- and S-nucleophiles
containing an active hydrogen atom with FcCH2OH.22 Later,
23
24
Yb(OTf)3 and Al(OTf)3 were used for this purpose. The
complex [RuCl(CO)(PPh3)(PNS-Me)] was found to be an active
catalyst for ferrocenylmethylation of amines.25 Then iron
complex [Fp][OTf] (Fp+ = [Fe(CO)2(Cp)]+) was employed for
coupling of C-, N-, P- and S-nucleophiles with FcCH2OH.26 More
recently, N-ferrocenylmethylation of sulfonamides with this
Among a variety of ferrocene derivatives, functionalized
molecules bearing the methylferrocene moiety are of special
interest owing to their useful properties. These compounds have
been shown to serve as potential drugs (anticancer,8 antitumor,9
antimalarial,10
antiplasmodial,11
antimycobacterial,12
antimicrobial,13 anticandidal14 and antiproliferative15 agents),
efficient ligands for catalysis,3,4 monomers for functional
polymers,16 ionic liquids17 and molecular sensors.18 Today, one of
the most efficient and straightforward approaches to access
methylferrocene derivatives is the reaction of various
nucleophiles with ferrocenylmethylating reagents,19 among which
[FcCH2NMe3]I, FcCH2NMe2 and FcCH2OH are the most
available. Although the methods for ferrocenylmethylation with
the first two reagents are quite well developed, they have some
principal limitations.19 In this regard, hydroxymethylferrocene is
27
alcohol catalyzed by {Cp*Ir-[6,6’-OH)2bpy](H2O)}[OTf]2 and
28
[Cp*IrCl2]2 was accomplished. It is relevant to note, however,
that the above metal catalysts are expensive and/or moisture
sensitive therefore requiring dry reaction conditions and special
apparatus. In this context, development of new metal-catalyst-
free ferrocenylmethylation methods is a challenging task in
organic chemistry.
As a contribution to this field, herein we report on the
unexpected ferrocenylmethylation of diverse O-, N-, S- and Se-
nucleophiles
(alcohols,
phenol,
1,2,4-triazole,
1,2,3-
a
more versatile reagent, however for its activation,
benzotriazole, methacrylic, dithio- and diselenophosphinic acids)
in an acid-catalyzed (CF3CO2H as catalyst) reaction with
available29 vinyloxymethylferrocene. This novel reaction was
stoichiometric amounts of Brønsted acids (HSO3F, HBr, HBF4,
HClO4, CH3CO2H, etc.)19,20 are usually required (with a few
———
Corresponding author. Tel.: +7-395-251-1431; fax: (+7) 3952419346; e-mail: boris_trofimov@irioch.irk.ru

2
Tetrahedron
ACCEPTED MANUSCRIPT
accidently found by us during the study of acid-catalized
Unlike aliphatic alcohols, allyl alcohol (2d) and 2,2,3,3-
addition of NuH species to vinyloxymethylferrocene that,
according to enol ether chemistry,30 should chemo- and
regioselectively allow the corresponding non-symmetric acetals.
Essentially, we describe a first example of formation of such
products as R–Nu in the reaction between vinyl ethers R–O–
CH=CH2 (exemplified by vinyloxymethylferrocene) and various
nucleophiles (NuH).
tetrafluoropropanol (2e) add to vinyl ether 1 more easily,
however the resulting adducts 3d,e are less stable under the
reaction conditions and tend to extrude acetaldehyde furnishing
the products of O-ferrocenylmethylation of the alcohols, viz.
5d,e. Thus, allyl alcohol (2d) at room temperature quantitatively
adds to vinyl ether 1 in 1.5 h (vs. 2 h for MeOH) to furnish
1
adduct 3d and side acetal 4 in 61 and 15% yields (entry 5). Н
NMR spectroscopic analysis of the reaction mixture shows
signals (broad singlets at 2.10 and 9.75 ppm) relative to the
protons of acetaldehyde. Further study has shown that conducting
the reaction at 45 оС leads to quantitative conversion of the
2. Results and Discussion
Reaction with alcohols and phenol
intermediate
Markovnikov
adduct
3d
into
Our experiments have shown that vinyloxymethylferrocene
(1) in the presence of catalytic amounts of CF3CO2H (2 mol%)
easily reacts with diverse alcohols 2a-e. The reaction conditions,
structures and ratios of isolated products are summarized in Table
1. As seen from these data, the reaction of 1 with methanol (2a)
selectively occurs at ambient temperature to afford the
Markovnikov adduct, isolated in 86% yield (entry 1). Under
similar conditions, alcohols with donating and bulkier
substituents, e.g. s-BuOH (2b) and t-BuOH (2c), add to 1 slower
(4 and 6 h, correspondingly vs. 2 h for MeOH), giving adducts
3b,c in 67 и 72% isolated yields (entries 2, 3). Also, in both
cases, 1,1-bis(ferrocenylmethoxy)ethane (4) as by-product was
isolated in 17 and 19% yield (entries 2, 3). Note that under the
allyloxymethylferrocene (5d), the yield of which being 55%
(entry 6). A similar result was obtained when the reaction was
performed at ambient temperature for 3 days. Noteworthy,
2,2,3,3-tetrafluoropropanol (2e) interacts with vinyl ether 1 under
mild conditions (r.t., 1.5 h) giving directly ether 5e along with
diferrocenylmethyl ether 6 (entry 8), the expected adduct 3e
being formed only in trace amounts (by 1H NMR spectroscopy).
We believe that the products of O-ferrocenylmethylation of
alcohols (5d,e) and other nucleophiles (vide infra) are formed
due to the elimination of acetaldehyde from the primary
Markovnikov adducts according to Scheme 1. The enhanced
stability of the initial Markovnikov adducts in the cases of
MeOH, s-BuOH and t-BuOH follows from DFT computation of
the fragmentation of 3a (model compound) to FcCH2OMe and
acetaldehyde (vide infra).
o
harsher conditions (45 C), the reaction with t-BuOH delivers
bis(ferrocenylmethyl) ether (6) as almost the only product (75%
yield), while the expected adduct 3c is formed just in traces
(entry 4).
Table
1
CF3CO2H-catalyzed reaction of vinyloxymethylferrocene with
alcoholsa
Scheme 1. The formation of O-ferrocenylmethylation products with alcohols.
In the reaction of
1 with phenol, the corresponding
Markovnikov adduct is so unstable that it cannot be detected by
NMR spectroscopy even when the reaction occurs at room
temperature. In this case, the fast elimination of acetaldehyde
from the initial adduct leads to the formation of
phenyloxymethylferrocene (7) in 70% isolated yield (Scheme 2).
As in the above cases, bis(ferrocenylmethyl) ether (6) was also
isolated in 24% yield.
Products (yield, %)b
T,
Time,
oC
Entry
R
h
3
4
5
6
5a
(none)
5b
(none)
5c
(none)
5c
(none)
5d
(trace)
5d
(55)
5d
(58)
5e
(38)
1
2
3
4
5
6
7
8
2
4
3a (86)
3b (67)
3c (72)
none
17
traces
traces
traces
75
Me (2a)
rt
rt
s-Bu (2b)
t-Bu (2c)
t-Bu (2c)
All (2d)
All (2d)
All (2d)
rt
45
rt
6
19
3c
(traces)
3
traces
15
1.5
5
3d (61)
traces
32
Scheme 2. CF3CO2H-catalyzed reaction of vinyloxymethylferrocene with
3d
(traces)
3d
(traces)
3e
45
rt
none
traces
traces
phenol.
72
31
All of the above products were purified by column
chromatography on basic alumina. It should be mentioned that
the isolation of acetals 3a-d and 4 was accompanied by their
partial hydrolysis with release of ferrocenylmethanol.
Compounds 3a-d are orange oils, soluble in common organic
solvents. In their 1H NMR spectra, each methyne proton, CHMe,
resonates as a quartet at 4.71-4.95 ppm, whereas Me protons
CHF2CF2CH2
rt
1.5
39
(2e)
(traces)
aReaction conditions: vinyl ether 1 (1 mmol), alcohol 2a-e (1 mmol),
CF3CO2H (2 mol%, as 0.025 M solution in DME), stirring.
bIsolated yields (after chromatographic purification).

3
appear as doublets at 1.29-1.31 ppm. The FT-IR spectra of 3a-d
contain four or five C–O acetal bands (1040-1155 cm-1) along
with bands of the ferrocene moiety (3090, 1450, 1100, 1010, 820,
480 cm-1).
in benzene, dichloromethane and DME. In contrast to all the
ACCEPTED MANUSCRIPT
previous products, in this case the initial Markovnikov adduct
appeared to be stable. The product ratio remained unchanged
upon storing the reaction mixture for about 1 month at room
temperature. During the chromatographic isolation of these
products on basic alumina, compounds 10, 11 and 4 as well as
ferrocenylmethanol were isolated in 40, 22, 12 and 10% yield,
correspondingly. The latter being resulted from the hydrolysis of
the adducts 4, 10 by trace water present in alumina.
The formation of bis(ferrocenylmethyl) ether (6) in the
reactions studied (Table 1, Scheme 2) most likely starts with
symmetrization of acetal 3 by the action of acid catalyst
(CF3CO2H) followed by elimination of acetaldehyde from the
resulting acetal 4 (Scheme 3).
Scheme 3. Tentative pathway for the formation of ether 6.
Scheme 5. CF3CO2H-catalyzed reaction of vinyl ether 1 with 1,2,4-triazole.
Reactions with 1H-triazoles
Taking into account the data of the easy non-catalyzed
addition of benzotriazole to ethyl vinyl ether under reflux in ССl4
(1.5 h),31 we have carried out the reaction of
vinyloxymethylferrocene (1) with benzotriazole under similar
conditions. However, no expected adduct was detected (not even
in traces) in the reaction mixture, although the reagents were
refluxed for as long as 3 h. Eventually, we have found that in the
presence of 4 mol% CF3CO2H, vinyl ether 1 adds benzotriazole
at ambient temperature (3 h) to afford a mixture of N1- and N2-
isomeric Markovnikov adducts 8a,b in the ratio of about 2:1 (1H
NMR spectroscopy) along with 1-ferrocenylmethyl-1H-1,2,3-
benzotriazole (9) (10% content in the reaction mixture). The
adducts 8a,b were not isolated in pure form due to their partial
Reaction with methacrylic acid
The addition of carboxylic acids to vinyloxymethylferrocene
(1) was studied on an example of the reaction with methacrylic
acid in the presence of catalytic amounts of CF3CO2H (1 mol%).
As the 1Н NMR spectroscopic monitoring has shown, the
reaction occurs via the formation of an unstable Markovnikov
adduct 12, which slowly eliminates acetaldehyde (Scheme 6) to
give ester 13. At ambient temperature this process is complete
within 10-15 h (1H NMR spectroscopic data), while upon heating
о
(45 С), the reaction takes for 2 h to afford only ester 13 and
acetaldehyde (detected by 1H NMR spectroscopy). The
compound 13 was isolated in 84% yield and its structure was
proved by 1Н and 13С NMR spectroscopy.
decomposition on chromatography (Al2O3) to
9
and
о
acetaldehyde. Upon heating (45 С, benzene, 3 h), the reaction
resulted in Markovnikov adducts 8a,b (in about equimolar
amounts) and compound 9 (Scheme 4). This mixture, upon
storage for several days, was quantitatively (1H NMR
spectroscopy) converted to benzotriazole 9, the isolated yield
being 91%.
Scheme 6. CF3CO2H-catalyzed reaction of vinyl ether 1 with methacrylic
acid.
Reaction with S-H and Se-H acids
We have observed that the dithiophosphinic acid 14 under
mild conditions (r.t., 3 h, Et2O as solvent) chemo- and
regioselectively interacts with vinyloxymethylferrocene (1) to
give only the Markovnikov adduct 15, the structure of which was
established by 1Н, 13С and 31Р NMR spectroscopy. However, the
adduct 15, owing to its instability, readily eliminates
acetaldehyde to form dithiophosphinate 16 (Scheme 7).
Furthermore, as a parallel reaction, this process takes place along
with the formation of primary Markovnikov adduct 15 (31P NMR
spectroscopic data). The complete conversion of the latter to
Scheme 4. CF3CO2H-catalyzed reaction of vinyl ether
1 with 1,2,3-
benzotriazole.
Unlike benzotriazole, 1,2,4-triazole regioselectively reacts
о
with vinyl ether 1 (5 mol% CF3CO2H, 40-45 C, 2-3 h) to give
the Markovnikov adduct 10 and 1-ferrocenylmethyl-1H-1,2,4-
triazole (11) along with a minor amount of 4 (Scheme 5). The
solvent nature does not significantly affect the reaction outcome:
approximately the same ratio (2.5:1) of 10 and 11 was obtained

4
Tetrahedron
ACCEPTED MANUSCRIPT
dithiophosphinate 15 was achieved by recrystallization of the
crude reaction product from hexane (upon boiling). Thus,
compound 16 was isolated in 81% yield as yellow crystals, the
structure of which was determined by X-ray diffractometry.
Fig. 1. Molecular structure of 16 (40% thermal ellipsoid). Selected bond
distances (Å) and angles (°): Cg(1)ꢀꢀꢀFe(1) 1.638, Cg(2)ꢀꢀꢀFe(1)1.648, S(1)–
P(1) 2.0937(5), S(2)–P(1) 1.9508(5), S(1)–C(6) 1.8467(15), P(1)–C(7)
1.8174(14), P(1)–C(15) 1.8219(13), S(2)–P(1)–S(1) 114.99(2), C(6)–S(1)–
P(1) 101.26(5), Cg(1)ꢀꢀꢀFe(1)ꢀꢀꢀCg(2) 178.95.
Scheme 7. Reaction of vinyl ether 1 with dithiophosphinic acid 14.
Likewise, the diselenophosphinic acid, generated in situ from
secondary phosphine 17 and elemental selenium (1:2 molar ratio,
95 oC), also without specially added catalyst reacts with
vinyloxymethylferrocene (Scheme 8). The 31Р NMR spectrum of
the reaction mixture shows two major peaks, 50.1 and 48.3 ppm
in a ratio of 9:1, assigned to Markovnikov adduct 18 and Se-ester
19, respectively. Upon the storage at room temperature, the
product ratio changes for reciprocal one (1:9). The Se-
ferrocenylmethyl diselenophosphinate 19 was isolated in 59%
yield and its structure was also determined by X-ray analysis.
Fig. 2. Molecular structure of 19 (30% thermal ellipsoid). Selected bond
distances (Å) and angles (°): Cg(1)ꢀꢀꢀFe(1) 1.640, Cg(2)ꢀꢀꢀFe(1) 1.652, Se(1)–
P(1) 2.0816(18), Se(2)–P(1) 2.2415(19), Se(2)–C(1) 1.997(6), P(1)–C(12)
1.800(7), P(1)–C(20) 1.826(6), Se(1)–P(1)–Se(2) 114.31(8), C(1)–Se(2)–P(1)
98.0(2), Cg(1)ꢀꢀꢀFe(1)ꢀꢀꢀCg(2) 179.26.
Theoretical study
Scheme 8. Reaction of vinyl ether 1 with diselenophosphinic acid.
With the aim to interpret the different chemoselectivity in the
reaction of vinyloxymethylferrocene (1) with the above
nucleophiles (formation of ferrocenylmethylation products versus
stable Markovnikov adducts), we have carried out preliminary
The structures of esters 16 and 19 are shown in Figures 1 and
2. Despite their similar structures, these compounds crystallized
in P-1 and P21/c space groups, correspondingly. Within both
molecules, the ferrocene unit has a nearly eclipsed conformation
with the bond lengths and angles typical for monosubstituted
ferrocenes. The phosphorus atoms, as expected, exhibit a
distorted tetrahedral geometry. The lengths of the P–S [2.0937(5)
Å] and P=S [1.9508(5) Å] bonds in 16 as well as the P–Se
[2.2415(19) Å] and P=Se [2.0816(18) Å] bonds in 19 are
consistent with literature values.32, 33
DFT
[B3LYP/6-311+G(d,p),
gas]
computations
for
fragmentation of Markovnikov adducts, key reaction
intermediates, to the corresponding ferrocenylmethylation
products (FcCH2Nu) and acetaldehyde. As model compounds,
adducts with methanol 3a and 1,2,4-triazole 10 having enhanced
stability, as well as the unstable adduct with methacrylic acid 12
have been chosen.
The computations reveal that elimination of acetaldehyde
from adduct 3a occurs through high-energy transition state TS1
leading to methoxymethylferrocene (5a). The corresponding free
energy profile is shown in Figure 3. The activation barrier of this
stage, being essentially an intramolecular 1,3-shift of the [FcCH2]
group to another oxygen atom, is 57.0 kcal/mol. Although taking
into account that solvent effect should decrease this value, the
barrier of such order is insuperable under common reaction

5
conditions. Similarly, extrusion of acetaldehyde from the adduct
ACCEPTED MANUSCRIPT
10 leading to 1-ferrocenylmethyl-1H-1,2,4-triazole (11) is
associated with overcoming a high activation barrier, 54.6
kcal/mol (TS2, Figure S1).
Fig. 4. Free energy profile for fragmentation of adduct 12 to 13 and
acetaldehyde.
Fig. 3. Free energy profile for fragmentation of 3a to 5a and acetaldehyde.
Thus, the significantly lower activation barrier of
fragmentation of adduct 12 (32.9 kcal/mol) in comparison with
that of adducts 3a and 10 (57.0 and 54.6 kcal/mol), explains why
the reaction of vinyloxymethylferrocene (1) with acids proceeds
directly to ferrocenylmethylation products, whereas interaction of
1 with MeOH, s-BuOH, t-BuOH and 1,2,4-triazole gives stable
Markovnikov adducts.
The fragmentation of the Markovnikov adduct with
methacrylic acid 12 to ester 13 and acetaldehyde may principally
occur either through a 1,5-intramolecular shift of the [FcCH2]
group to carbonyl oxygen (C=O) or through a 1,3-shift of this
group to another oxygen atom (Scheme 9). While the first
pathway is less favorable (activation barrier being 37.9 kcal/mol,
Figure S2), the second one is quite plausible (Figure 4). This is a
thermodynamically preferable one-step process including
transition state (TS3) with activation barrier of 32.9 kcal/mol.
The further transformation of TS3 leads to the weakly bonded
complex of O-ferrocenylmethyl methacrylate (13) with
acetaldehyde. The overall change in the Gibbs free energy of
reaction being –12.6 kcal/mol.
3. Conclusion
In summary, we have found and the elaborated
ferrocenylmethylation of diverse O-, N-, S- and Se-nucleophiles
(alcohols, carbonic acids, triazoles, thio- and selenophosphinic
acids)
based
on
the
reaction
with
available
vinyloxymethylferrocene. The latter under mild acid-catalyzed
(1-5 mol% CF3CO2H as catalyst) conditions easily adds these
nucleophiles to afford initial Markovnikov adducts, which then
readily eliminate acetaldehyde to give the corresponding
ferrocenylmethylation products in good to high yields.
Exceptions are methanol, butyl alcohols as well as 1,2,4-triazole,
which
form
stable
Markovnikov
adducts
with
vinyloxymethylferrocene. The study establishes for the first time
a novel type of reactivity of vinyl ethers R–O–Vin, i.e., when the
latter reacting with Nu–H species produced products of R–Nu
type. Furthermore, the results obtained contribute to the basic
chemistry of ferrocene providing a synthetically valuable
approach to ferrocenylmethylation of various nucleophiles
(including biologically important molecules).
4. Experimental section
4.1. General
1H NMR spectra were recorded with Bruker DPX 400 and
Bruker AV-400 spectrometers (400.13 MHz); chemical shifts are
expressed with respect to residual protonated solvent (δ = 7.27
ppm for CHCl3), which served as an internal standard. 13C NMR
spectra were recorded with a Bruker DPX 400 (100.62 MHz)
instrument; chemical shifts are expressed with respect to the
deuterated solvent (δ = 77.0 ppm for CDCl3). The 31P NMR
spectra were recorded on a Bruker DPX 400 spectrometer
(161.98 MHz, respectively) and referenced to H3PO4 (31P NMR).
Coupling constants (J) are reported in Hz. FT-IR Spectra were
recorded on a Bruker Vertex 70 spectrometer. The C, H, N
microanalyses were performed on a Flash EA 1112 elemental
analyzer, while the P and Fe contents were determined by
Scheme 9. Two possible mechanisms for fragmentation of adduct 12.

6
Tetrahedron
combustion methods. Melting points (uncorrected) were
starting vinyl ether 1. Then, the reaction mixture was stirred at rt
ACCEPTED MANUSCRIPT
determined on a Kofler micro hot stage.
for additional 3 h. Further treatment was performed in the same
Vinyloxymethylferrocene
(1)
was
synthesized
by
way as described for compound 5d.
KOH/DMSO-catalyzed vinylation of ferrocenylmethanol with
acetylene according to reported procedure.34 Alcohols 2a-e were
dried over 4.0 Å molecular sieves prior to use. Dithiophosphinic
acid 1435 and secondary phosphine 1736 were prepared as
described in the literature. All the solvents used were purified and
dried by standard methods. Basic Al2O3 and n-hexane/Et2O as
eluent were used for column chromatography. All reactions were
monitored by TLC on silica gel plates 60 F254 (50% n-
hexane/Et2O). Visualization was done with iodine vapor.
4.3.4. Synthesis of phenyloxymethylferrocene (7)
Following
the
typical
procedure
for
5d,
vinyloxymethylferrocene (242 mg, 1 mmol), phenol (94 mg, 1
mmol) and a catalytic amount of CF3CO2H (2 mol%) were stirred
at ambient temperature for 1.5 h until the complete consumption
of the starting vinyl ether 1. Then, the reaction mixture was
stirred at rt for additional 3 h. Further treatment was performed as
described for compound 5d.
4.2. Crystallography
4.3.5.
Procedure
for
the
preparation
and
of
1-[1-
2-[1-
(ferrocenylmethoxy)ethyl]-1H-
Single crystals of 16 and 19 were obtained by slow
evaporation of their hexane solutions at ambient temperature. The
data were collected on a Bruker Kappa Apex II CCD
diffractometer using φ,ω-scans of narrow (0.5°) frames with
MoKα radiation (λ = 0.71073 Å) and a graphite monochromator.
The structures were solved by direct methods and refined by full-
matrix least-squares method against all F2 in anisotropic
approximation using the SHELX-97 programs set.37 The
hydrogen atoms positions were calculated with the riding model.
Absorption corrections were applied using the empirical
multiscan method with the SADABS program.38
(ferrocenylmethoxy)ethyl]-2H-1,2,3-benzotriazole (8a,b)
To a solution of vinyloxymethylferrocene (242 mg, 1 mmol)
in DME (2 mL), 1,2,3-benzotriazole (119 mg, 1 mmol) and
CF3CO2H (5 mg, 4 mol%) were added. The reaction mixture was
stirred at ambient temperature for 3 h until the vinyl ether 1 had
disappeared. The mixture was quenched with NaHCO3 (1 %
solution, 10 mL) and extracted with diethyl ether (4×5 mL). The
organic layer was dried over Na2SO4 and concentrated under
reduced pressure. The residue (303 mg), a mixture of α-adducts
8a,b and 1-ferrocenylmethyl-1H-1,2,3-benzotriazole (9) (molar
1
CCDC 994803 (16), 1450492 (19) contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
ratio 9:1 by H NMR spectroscopy), was purified by column
chromatography on Al2O3 using hexane, then hexane/Et2O (1:1,
v/v) as the eluent to afford an inseparable mixture of 8a and 8b
(68:32, purity ~95% by 1H NMR spectroscopy).
4.3. Synthesis
4.3.6. Procedure for the preparation of 1-ferrocenylmethyl-1H-
1,2,3-benzotriazole (9)
4.3.1.
General
procedure
for
synthesis
of
[1-
(alkoxy)ethoxy]methylferrocene 3a-d
To a stirred solution of vinyloxymethylferrocene (1) (242 mg,
1 mmol) in benzene (2 mL), 1,2,3-benzotriazole (119 mg, 1
mmol) and CF3CO2H (5 mg, 4 mol%) were added. The reaction
To a mixture of vinyloxymethylferrocene (1) (242 mg, 1
mmol) and alcohol 2a-d (1 mmol), a solution of CF3COOH [2%
in 1,2-dimethoxyethane (DME), 0.1 mL, ~ 2 mol%] was added.
The resulting mixture was stirred at ambient temperature for 1.5-
6 h (Table 1). After complete conversion of starting vinyl ether 1
(TLC control), K2CO3 (14 mg, 0.1 mmol) and diethyl ether (2
mL) were added and the mixture was stirred for ~0.5 h. After
removal of volatiles, the crude residue was separated by column
chromatography (basic Al2O3, 1.5 × 10 cm): Markovnikov adduct
3a-d was washed off first with hexane, and then acetal 4 and
ferrocenylmethanol were washed off with hexane/diethyl ether
(1:1) and diethyl ether, respectively.
o
mixture was stirred at 45 C for 3 h and then the solvent was
removed under reduced pressure. The crude product, ca.
equimolar mixture of products 8a,b and 9 (by 1H NMR
spectroscopy), was allowed to stay 3 days until the complete
consumption of the Markovnikov adducts 8a,b. The mixture was
quenched with NaHCO3 (1 % solution, 10 mL) and extracted
with diethyl ether (4×5 mL). The organic layer was dried over
Na2SO4. Column chromatography (basic Al2O3, eluent
hexane/Et2O 1:1) of the crude residue after removal of the
solvent gave 9.
4.3.7. Reaction of vinyloxymethylferrocene with 1,2,4-triazole
4.3.2. Synthesis of (2-propenyloxy)methylferrocene (5d)
A mixture of vinyloxymethylferrocene (242 mg, 1 mmol),
1,2,4-triazole (69 mg, 1 mmol) and CF3CO2H (6 mg, 5 mol%) in
dry DME (2 mL) was stirred at 45 С for 2 h. After removal of
the volatiles, the residue was separated by column
chromatography (Al2O3, 1.5×10 cm) using hexane/Et2O (1:1,
v/v), then Et2O as the eluent to afford acetal 4 (27 mg, yield
12%), products 10 and 11, and ferrocenylmethanol (21 mg,
10%).
To a mixture of vinyloxymethylferrocene (242 mg, 1 mmol)
and allyl alcohol (2d) (58 mg, 1 mmol), a solution of CF3COOH
(2% in DME, 0.1 mL, 2 mol%) was added. The resulting mixture
o
o
was stirred for 5 h at 45 C and then quenched with 1% aqueous
solution NaHCO3 (10 mL), and extracted with diethyl ether (5 ×
5 mL). The extract was dried over Na2SO4. The residue after
removing of the volatiles was passed through a chromatographic
column (basic Al2O3, 1.5 × 10 cm): the first product 5d was
washed off with hexane, and then ferrocenylmethyl ether (6) was
washed with hexane/diethyl ether, 3:1.
4.3.8. Reaction of vinyloxymethylferrocene with dithiophosphinic
acid 14
4.3.3. Synthesis of (2,2,3,3-tetrafluoropropoxy)methylferrocene
(5e)
To a solution of vinyloxymethylferrocene (242 mg, 1 mmol)
in diethyl ether (5 mL), acid 14 (306 mg, 1 mmol) was added and
the solution was stirred at ambient temperature for 3 h. Then the
reaction mixture was passed through a layer of Al2O3 (0.5 cm),
the latter was additionally washed with diethyl ether (5 mL). The
volatiles were removed in vacuo to give product, consisting of
compound 15 with an admixture of 16 (molar ratio ≈ 7 : 1 by 31P
Following
the
typical
procedure
for
3a,
vinyloxymethylferrocene (242 mg,
1
mmol), 2,2,3,3-
tetrafluoropropanol (2e) (132 mg, 1 mmol) and a catalytic
amount of CF3CO2H (2 mol%) were stirred at ambient
temperature for 1.5 h until the complete consumption of the

7
NMR spectroscopy). The subsequent recrystallization of ester 15
(refluxing in hexane) gave compound 16 as yellow solid.
Orange oil. Yield: 179 mg (60%). Rf = 0.62 (hexane/Et2O,
ACCEPTED MANUSCRIPT
1:1). FT-IR (film): ṽ = 3088, 1455, 1012, 822, 482 (Fc), 1142,
1123, 1105, 1097, 1040 (OCHO), 1618 (C=C) cm-1. H NMR
1
4.3.9.
Reaction
of
vinyloxymethylferrocene
with
3
(400.13 MHz, CDCl3): δ = 1.32 (d, J = 5.4 Hz, 3 H, Me), 3.98-
diselenophosphinic acid (generated in situ from phosphine 17
and selenium)
4.14 (m, 9 H, OCH2CH=, C5H5, Hβ in Fc), 4.21 (br s, 2 H, Hα in
Fc), 4.30, 4.38 (2d, 2J = 11.3 Hz, each 1 H, OCH2Fc), 4.81 (q, 3J
= 5.4 Hz, 1 H, HCMe), 5.18 (dd, 3J = 10.4 Hz, 4J = 1.7 Hz, 1 H,
=CHcis), 5.29 (dd, 3J = 17.2 Hz, 4J = 1.7 Hz, 1 H, =CHtrans), 5. 94
Bis(2-phenethyl)phosphine (17) (242 mg, 1 mmol) and
powdered grey selenium (158 mg, 2.0 mmol) were added
consecutively to a solution of 1 (242 mg, 1 mmol) in 1,4-dioxane
(8 mL) at ambient temperature. The suspension was stirred at 95-
100 oC until dissolution of the selenium powder (ca. 1 h) to give
an orange transparent solution consisting of corresponding
Markovnikov adduct 18 in an admixture with Se-ester 19 in the
molar ratio of 9:1 (by 31P NMR spectroscopy, δP 50.1 and 48.3
ppm). After vacuum treatment of the reaction mixture at 50–60
°C (1–2 mm Hg) adduct 18 was converted to Se-ester 19. The
latter was purified by column chromatography (basic Al2O3, 1.5
× 10 cm, hexane as eluent).
(ddt, 3J = 17.2 Hz, 3J = 10.4 Hz, 3J = 5.4 Hz, 1 H, CH=CH2). 13
C
NMR (100.62 MHz, CDCl3): δ = 19.6 (MeCH), 63.2 (CH2Fc),
65.5 (OCH2), 68.3 (Cβ in Fc), 68.4 (C5H5), 69.1, 69.2 (Cα in Fc),
83.5 (Ci in Fc), 98.2 (MeCH), 116.5 (CH2=), 134.8 (CH=CH2).
Anal. Сalcd. for C16H20FeO2 (300.17): С, 64.02; Н, 6.72; Fe,
18.60. Found: C, 64.06; Н, 6.44; Fe, 18.90.
4.4.5. 1,1-Bis(ferrocenylmethoxy)ethane (4)
o
Yellow solid, mp 80-82 C. Rf = 0.56 (hexane/Et2O, 1:1). FT-
IR (film): ν = 3093, 1105, 1002, 819, 493, 482 (Fc), 1123, 1105,
1097, 1040 (OCHO) cm-1. H NMR (400.13 MHz, CDCl3): δ =
1
4.4. Characterization data for synthesized compounds
3
1.33 (d, J = 4.8 Hz, 3 H, Me), 4.15 (s, 10 H, 2C5H5), 4.18 (s, 4
2
4.4.1. [1-(Methoxy)ethoxy]methylferrocene (3a)
H, Hβ in Fc), 4.26 (br s, 4 H, Hα in Fc), 4.31, 4.39 (2d, J = 11.0
Hz, each 2 H, OCH2Fc), 4.83 (q, J = 4.8 Hz, 1 H, HCMe). 13C
3
Orange oil. Yield: 236 mg (86%). Rf = 0.51 (hexane/Et2O,
1:1). FT-IR (film): ṽ = 3094, 1449, 1013, 819, 483 (Fc), 1140,
1125, 1106, 1091, 1040 (OCHO) cm-1.1H NMR (400.13 MHz,
NMR (100.62 MHz, CDCl3): δ = 19.8 (Me), 63.0 (CH2Fc), 68.4
(C5H5), 69.3 (Cβ in Fc), 69.4 (Cα in Fc), 83.7 (Ci in Fc), 98.0
(CH). Anal. Сalcd. for C24H26Fe2O2 (458.15): С, 62.92; Н, 5.72;
Fe, 24.38. Found: C, 63.02; Н, 5.78; Fe, 24.09.
3
CDCl3): δ = 1.29 (d, J = 5.4 Hz, 3 H, Me), 3.31 (s, 3 H, OMe),
4.14 (br s, 7 H, C5H5, Hβ in Fc), 4.23 (s, 2 H, Hα in Fc), 4.27, 4.38
(2d, 2J = 11.1 Hz, each 1 H, OCH2Fc), 4.71 (q, 3J = 5.4 Hz, 1 H,
HCMe). 13C NMR (100.62 MHz, CDCl3): δ = 18.9 (Me), 51.5
(OMe), 68.2 (Cβ in Fc), 68.4 (C5H5), 69.1 (Cα in Fc), 71.6
(CH2Fc), 83.6 (Ci in Fc), 99.1 (CH). Anal. Сalcd. for C14H18FeO2
(274.14): С, 61.34; Н, 6.62; Fe, 20.37. Found: C, 61.66; Н, 6.44;
Fe, 20.81.
4.4.6. (2-Propenyloxy)methylferrocene (5d)
Yellow wax-like solid. Yield: 141 mg (55%). Rf = 0.76
(hexane/Et2O, 1:1). FT-IR (film): ṽ = 3090, 1001, 822, 483 (Fc),
1618 (C=C) cm-1. 1H NMR (400.13 MHz, CDCl3): δ = 3.99 (d, 3J
= 5.1 Hz, 2 H, OCH2CH=), 4.14 (s, 5 H, C5H5), 4.16 (br s, 2 H,
Hβ in Fc), 4.25 (br s, 2 H, Hα in Fc), 4.30 (s, 2 H, OCH2Fc), 5.19
3
3
4.4.2. [1-(1-Methylpropoxy)ethoxy]methylferrocene (3b)
(d, J = 10.3 Hz, 1 H, =CHcis), 5.28 (d, J = 17.4 Hz, 1 H,
=CHtrans), 5.91 (ddt, 3J = 17.4 Hz, 3J = 10.3 Hz, 3J = 5.1 Hz, 1 H,
CH=CH2). 13C NMR (100.62 MHz, CDCl3): δ = 68.3 (CH2Fc),
68.4 (C5H5, Cβ in Fc), 69.4 (Cα in Fc), 70.7 (CH2CH=), 83.3 (Ci
in Fc), 116.8 (CH2=), 134.9 (CH=CH2). Anal. Сalcd. for
C14H16FeO (256.12): С, 65.65; Н, 6.30; Fe, 21.80. Found: C,
65.76; Н, 6.44; Fe, 21.90. Spectroscopic data are in full
agreement with those previously reported.39
Orange oil. Yield: 213 mg (67%). An inseparable 1:1 mixture
of two diastereoisomers. Rf = 0.65 (hexane/Et2O, 1:1). FT-IR
(film): ṽ = 3096, 1456, 1021, 819, 484 (Fc), 1155, 1106, 1087,
1
1040 (OCHO) cm-1. H NMR (400.13 MHz, CDCl3): δ = 0.90,
3
3
0.98 (2t, J = 7.3 Hz, each 1.5 H, MeCH2), 1.13, 1.22 (2d, J =
3
6.1 Hz, each 1.5 H, MeCHCH2), 1.33 (d, J = 5.4 Hz, 3 H,
MeCHO), 1.43-1.66 (m, 2 H, CH2Me), 3.60-3.69 (m, 1 H,
MeCHEt), 4.14 (br s, 7 H, C5H5, Hβ in Fc), 4.22, 4.24 (2br s, each
4.4.7. (2,2,3,3-Tetrafluoropropoxy)methylferrocene (5e)
2
1 H, Hα in Fc), 4.30, 4.40 (2d, J = 11.0 Hz, each 1 H, OCH2Fc),
Orange solid, mp 54-55 oC (hexane). Yield: 130 mg (39%). Rf
= 0.70 (hexane/Et2O, 1:1). FT-IR (KBr): ṽ = 3100, 1405, 1106,
1001, 834, 483 (Fc) cm-1.1H NMR (400.13 MHz, CDCl3): δ =
4.80, 4.83 (2q, 3J = 5.4 Hz, 1 H, HCMe). 13C NMR (100.62 MHz,
CDCl3): δ = 9.6, 10.2 (MeCH2), 19.6, 20.7 (MeCHCH2), 20.5
(MeCHO), 29.3, 30.2 (CH2Me), 62.4 (CH2Fc), 68.2 (C5H5), 68.3,
69.1 (C5H4), 72.5, 73.6 (CHO), 83.8 (Ci in Fc), 97.0, 98.2
(HCMe). Anal. Сalcd. for C17H24FeO2 (316.22): С, 64.57; Н,
7.65; Fe, 17.66. Found: C, 64.69; Н, 7.97; Fe, 17.59.
3
3.78 (t, J = 12.4 Hz, 2 H, OCH2), 4.16 (br s, 7 H, C5H5, Hβ in
Fc), 4.20, 4.24 (2 br s, 2 H, Hα in Fc), 4.41 (s, 2 H, OCH2Fc),
5.93 (tt, 2J = 53.3 Hz, 3J = 5.1 Hz, 1 H, HCF2). 13C NMR (100.62
2
MHz, CDCl3): δ = 66.4 (t, J = 28.9 Hz, CH2O), 68.5 (C5H5),
4.4.3. [1-(tert-Butoxy)ethoxy]methylferrocene (3c)
68.8 (Cα in Fc), 69.4, (Cβ in Fc), 70.5 (CH2O), 81.6 (Ci in Fc),
109.1 (tt, 1J = 248.8 Hz, 2J = 33.9 Hz, CF2), 115.2 (tt, 1J = 250.0
2
Orange oil. Yield: 229 mg (72%). Rf = 0.64 (hexane/Et2O,
1:1). FT-IR (film): ṽ = 3095, 1473, 1001, 818, 484 (Fc), 1144,
Hz, J = 26.4 Hz, CF2). Anal. Сalcd. for C14H14F4FeO (330.10):
С, 50.94; Н, 4.27; Fe, 16.92. Found: C, 50.69; Н, 4.42; Fe, 16.80.
1
1120, 1106, 1091, 1040 (OCHO) cm-1. H NMR (400.13 MHz,
3
4.4.8. Bis(ferrocenylmethyl)ether (6)
CDCl3): δ = 1.25 (s, 9 H, Me3C), 1.30 (d, J = 5.4 Hz, 3 H, Me),
4.11-4.12 (nr m, 7 H, C5H5, Hβ in Fc), 4.20, 4.21 (2br s, 2 H, Hα in
Fc), 4.25, 4.31 (2d, 2J = 11.0 Hz, each 1 H, OCH2Fc), 4.95 (q, 3J
= 5.4 Hz, 1 H, HCMe). 13C NMR (100.62 MHz, CDCl3): δ = 21.9
(MeCHO), 28.8 (3 Me in t-Bu), 61.3 (CH2Fc), 68.1, 68.2 (Cα in
Fc), 68.4 (C5H5), 69.0 (Cβ in Fc), 73.7 (C in t-Bu), 84.2 (Ci in
Fc), 93.5 (HCMe). Anal. Сalcd. for C17H24FeO2 (316.22): С,
64.57; Н, 7.65; Fe, 17.66. Found: C, 64.66; Н, 7.44; Fe, 17.81.
o
o
Orange solid, mp 129-131 C {ref.40 126-128 C}. Rf = 0.55
(hexane/Et2O, 1:1). FT-IR (KBr): ṽ =3103, 3092, 1103, 1000,
819, 497, 483 (Fc) cm-1. H NMR (400.13 MHz, CDCl3): δ =
1
4.13 (s, 10 H, C5H5), 4.15 (t, 3J = 1.7 Hz, 4 H, Hβ in Fc), 4.24 (t,
3J = 1.7 Hz, 4 H, Hα in Fc), 4.28 (s, 4 H, OCH2Fc). 13C NMR
(100.62 MHz, CDCl3): δ = 67.9 (CH2Fc), 68.3 (Cβ in Fc), 68.4
(C5H5), 69.3 (Cα in Fc), 83.7 (Ci in Fc). Anal. Сalcd. for
C22H22Fe2O (414.10): С, 63.81; Н, 5.35; Fe, 26.97. Found: C,
4.4.4. [1-(2-Propenyloxy)ethoxy]methylferrocene (3d)

8
Tetrahedron
ACCEPTED MANUSCRIPT
4.4.13. Ferrocenylmethyl-1H-1,2,4-triazole (11)
63.96; Н, 5.48; Fe, 26.49. Spectroscopic data are in full
agreement with those previously reported.41
Yellow solid, mp 82 C (hexane) {ref.42 81.2 C). Yield: 59
mg (22%). Rf = 0.10 (Et2O). H NMR (400.13 MHz, CDCl3):δ =
o
o
1
4.4.9. Phenyloxymethylferrocene (7)
4.18 (s, 5 H, C5H5), 4.23 (t, 3J = 1.7 Hz, 2 H, Hβ in Fc), 4.29 (t, 3J
= 1.7 Hz, 2 H, Hα in Fc), 5.12 (s, 2 H, CH2), 7.93, 7.98 (2s, each
1 H, CH3,5). Anal. Сalcd. for C13H13FeN3 (267.11): С, 58.46; Н,
4.91; N, 15.73. Found: C, 58.32; Н, 4.86; N, 15.89.
Spectroscopic data are in full agreement with those previously
reported.42
Yellow crystals, mp 135-136 oC (hexane). Yield: 204 mg
(70%). Rf = 0.71 (hexane/Et2O, 1:1). FT-IR (KBr): ṽ = 3038,
1430, 1104, 1000, 814, 504, 485 (Fc) cm-1. H NMR (400.13
1
MHz, CDCl3): δ = 4.20 (s, 7 H, C5H5, Hβ in Fc), 4.34 (br s, 2 H,
Hα in Fc), 4.81 (s, 2 H, OCH2Fc), 6.95-6.99 (m, 3 H, o,p-H in
Ph), 7.28-7.32 (m, 2 H, m-H in Ph). 13C NMR (100.62 MHz,
CDCl3):δ = 66.4 (CH2O), 68.5 (C5H5, Cα in Fc), 69.0 (Cβ in Fc),
82.7 (Ci in Fc), 114.7 (o-C in Ph), 120.7 (p-C in Ph), 129.3 (m-C
in Ph), 158.7 (i-C in Ph). Anal. Сalcd. for C17H16FeO (292.15):
С, 69.89; Н, 5.52; Fe, 19.11. Found: C, 69.62; Н, 5.46; Fe, 18.94.
Spectroscopic data are in full agreement with those previously
reported.41
4.4.14. O-Ferrocenylmethyl 2-methacrylate (13)
Yellow crystals, mp 76-77 oC (hexane) {ref.42 76.5 oC). Yield:
238 mg (84%). Rf = 0.65 (hexane/Et2O, 1:1). FT-IR (KBr): ṽ =
1408, 1104, 1002, 813, 483 (Fc), 1632 (C=C), 1710 (C=O) cm-1.
1H NMR (400.13 MHz, CDCl3): δ = 1.96 (s, 3 H, Me), 4.18 (br s,
7 H, C5H5, Hβ in Fc), 4.30 (s, 2 H, Hα in Fc), 4.97 (s, 2 H,
OCH2Fc), 5.56 (s, 1 H, =CHcis), 6.11 (s, 1 H, =CHtrans). 13C NMR
(100.62 MHz, CDCl3): δ = 18.3 (Me), 62.9 (OCH2), 68.5 (C5H5),
68.6 (Cα in Fc), 69.3 (Cβ in Fc), 81.6 (Ci in Fc), 125.5 (CH=),
136.3 (C=), 167.2 (C=O). Anal. Сalcd. for C15H16FeO2 (284.13):
С, 63.41; Н, 5.68; Fe, 19.65. Found: C, 63.76; Н, 5.68; Fe, 19.88.
Spectroscopic data are in full agreement with those previously
reported.42
4.4.10. Mixture of 1-[1-(ferrocenylmethoxy)ethyl]-1H- (8a) and
2-[1-(ferrocenylmethoxy)ethyl]-2H-1,2,3-benzotriazole (8b)
Orange wax-like solid. Ratio of 8a/8b is 68:32 (1H NMR).
Combined yield: 224 mg (62%). Rf = 0.36 (hexane/Et2O, 1:1).
FT-IR (film): ṽ = 3093, 1411, 1105, 1001, 816, 482 (Fc), 1150,
1120, 1076, 1040 (OCHN) cm-1. H NMR (400.13 MHz,
CDCl3):δ = 1.82 (d, 3J = 6.1 Hz, 3 H, Me, major), 1.87 (d, 3J = 6.0
Hz, 3 H, Me, minor), 4.03-4.31 (m, 11 H, OCH2, C5H5, Hα, Hβ in
Fc, major + minor), 6.16 (q, J = 6.0 Hz, 1 H, NCHO, minor),
6.35 (q, J = 6.1 Hz, 1 H, NCHO, major), 7.38-7.51 (m, 4 H,
BTA, major + minor), 7.80 (d, J = 8.3 Hz, 1 H, BTA, major),
7.94-7.95 (m, 2 H, Btz, minor), 8.12 (d, J = 8.3 Hz, 1 H, BTA,
4.4.15. S-[1-(Ferrocenylmethoxy)ethyl]diphenethyldithio-
phosphinate (15)
3
3
3
This compound was not isolated in pure state. Its structure was
determined from a mixture of 15 and 16 (molar ratio of ca. 7 : 1)
obtained after flash-chromatography. Yellow wax-like solid.
Yield: 472 mg (77%). FT-IR (film): ṽ = 3085, 1105, 1000, 820
(Fc), 1156, 1100 sh, 1040 (OCHS), 750 (P-C), 698 (P=S), 494
(P-S) cm-1. 1H NMR (400.13 MHz, CDCl3): δ = 1.79 (d, 3 H, 3J =
5.9 Hz, Me), 2.28-2.54 (m, 4 H, PCH2), 2.97-3.16 (m, 4 H,
PhCH2), 4.15-4.16 (nr m, 7 H, C5H5, Hβ in Fc), 4.27, 4.33 (2br s,
3
major). 13C NMR (100.62 MHz, CDCl3): δ = 21.0 (Me, major),
21.5 (Me, minor), 66.7 (CH2O, major), 67.1 (CH2O, minor), 68.3
(C5H5, major + minor), 68.6, 69.7 (Cα, Cβ in Fc, minor), 68.8,
69.1 (Cα, Cβ in Fc, major), 81.2 (Ci in Fc, major + minor), 85.6
(NCHO, major), 89.6 (NCHO, minor), 111.3 (2C, BTA, minor),
118.5 (2C, BTA, minor), 120.0, 124.2, 126.6, 127.3 (BTA,
major), 131.0 (BTA, major), 144.0 (2C, BTA, minor), 146.8
(BTA, major). Anal. Сalcd. for C19H19FeN3O (361.22): С, 63.18;
Н, 5.30; N, 11.63. Found: C, 63.03; Н, 5.35; N, 11.98.
2
each 1 H, Hα in Fc), 4.45, 4.60 (2d, J = 11.0 Hz, each 1 H,
3
3
OCH2), 5.48-5.56 (dq, J = 10.8 Hz, J = 5.9 Hz, 1 H, OCHS),
7.27-7.36 (m, 10 H, Ph). 13C NMR (100.62 MHz, CDCl3): δ =
25.6 (Me), 29.0, 29.3 (PhCH2), 39.6, 39.8 (2d, 1J = 50.0 and 48.7
Hz, PCH2), 67.4 (OCH2), 68.6 (C5H5), 68.7, 69.1, 69.5, 69.6
(C5H4), 82.5 (Ci in Fc), 86.9 (OCHS), 126.6 (p-C in Ph), 128.4
4.4.11. 1-Ferrocenylmethyl-1H-1,2,3-benzotriazole (9)
o
o
Orange solid, mp 134-136 C (hexane) {ref.43 134-135 C}.
3
(o-C in Ph), 128.8 (m-C in Ph), 140.4 (d, J = 16.4 Hz, i-C in
Yield: 288 mg (91%). Rf = 0.25 (hexane/Et2O, 1:1). FT-IR (KBr):
Ph). 31P NMR (161.98 MHz, CDCl3): δ = 72.03.
ṽ = 3091, 1103, 1000, 813, 482 (Fc) cm-1. H NMR (400.13
1
4.4.16. S-Ferrocenylmethyldiphenethyldithiophosphinate (16)
MHz, CDCl3):δ = 4.17 (br s, 2 H, C5H4), 4.19 (s, 5 H, C5H5), 4.32
3
(br s, 2 H, C5H4), 5.61 (s, 2 H, CH2Fc), 7.35, 7.45 (2t, J = 7.6
Yellow solid, mp 77-78 oC (hexane). Yield: 408 mg (81%). Rf
= 0.67 (hexane/Et2O, 1:1). FT-IR (KBr): ṽ =3085, 1105, 1000,
Hz, each 1 H, CH5,6), 7.52 (d, 3J = 8.3 Hz, 1 H, CH4), 8.05 (d, 3J
= 8.3 Hz, 1H, CH7). 13C NMR (100.62 MHz, CDCl3): δ = 47.6
(CH2Fc), 68.2, 68.3 (C5H4), 68.4 (C5H5), 81.3 (Ci in Fc), 109.2
(C7), 119.4 (C4), 123.2 (C6), 126.6 (C5), 132.0 (C9), 145.5 (C8).
Anal. Сalcd. for C17H15FeN3 (317.17): С, 64.38; Н, 4.77; N,
13.25. Found: C, 63.97; Н, 4.36; N, 13.02. Spectroscopic data
are in full agreement with those previously reported.9a
1
821, 482 (Fc), 749 (P-C), 698 (P=S), 498 (P-S) cm-1. H NMR
(400.13 MHz, CDCl3):δ = 2.26-2.33 (m, 4 H, PCH2), 2.84-3.04
(m, 4 H, PhCH2), 4.02, 4.05 (2s, each 1 H, Hα in Fc), 4.16 (s, 2 H,
Hβ in Fc), 4.19 (s, 5 H, C5H5), 4.33 (s, 2 H, SCH2), 7.14-7.31 (m,
10 H, Ph). 13C NMR (100.62 MHz, CDCl3): δ = 29.1 (СH2Ph),
1
31.8 (SCH2), 38.7 (d, J = 49.1 Hz, PCH2), 68.4 (C5H4), 68.9
4.4.12. 1-(Ferrocenylmethoxy)ethyl]-1H-1,2,4-triazole (10)
(C5H5), 69.1 (C5H4), 82.2 (Ci in Fc), 126.4 (p-C in Ph), 128.2 (o-
3
C in Ph), 128.6 (m-C in Ph), 140.4 (d, J = 16.4 Hz, i-C in Ph).
o
Yellow solid, mp 65 C (hexane). Yield: 125 mg (40%). Rf =
31P NMR (161.98 MHz, CDCl3):δ = 73.70. Anal. Calcd. for
C27H29FePS2 (504.52): C, 64.28; H, 5.79; Fe, 11.07; P, 6.14.
Found: C, 64.10; H, 5.46; Fe, 10.70; P, 5.70.
0.17 (Et2O). FT-IR (KBr): ṽ = 3096, 1102, 1003, 822, 483 (Fc),
1142, 1116, 1049 (OCHN) cm-1. 1H NMR (400.13 MHz,
3
CDCl3):δ = 1.67 (d, J = 6.1 Hz, 3 H, Me), 4.10 (s, 5 H, C5H5),
4.16-4.18 (m, 4 H, C5H4), 4.22, 4.31 (2d, 2J = 11.4 Hz, each 1 H,
4.4.17. Se-[1-(Ferrocenylmethoxy)ethyl]diphenethyldiseleno-
phosphinoate (18)
3
CH2O), 5.68 (q, J = 6.1 Hz, 1 H, CHMe), 8.00, 8.27 (2s, each 1
H, CH3,5). 13C NMR (100.62 MHz, CDCl3): δ = 21.6 (Me), 66.7
(CH2O), 68.5 (C5H5), 68.7, 69.0, 69.2, 69.6 (C5H4), 80.8 (Ci in
Fc), 84.3 (NCH), 140.7 (C5H), 150.9 (C3H). Anal. Сalcd. for
C15H17FeN3O (311.16): С, 57.90; Н, 5.51; N, 13.50. Found: C,
57.68; Н, 5.36; N, 13.39.
was identified by 31P NMR spectroscopy. 31P NMR (161.98
MHz, 1,4-dioxane): δ = 50.15 (satellites: 1JP=Se = 755 Hz, 1JP-Se
=
351 Hz).
4.4.18. Se-Ferrocenylmethyldiphenethyldiselenophosphinate (19)

9
Orange solid, mp 80-82 oC (hexane). Yield: 353 mg (59%). Rf
9.
(a) Snegur, L. V.; Nekrasov, Yu. S.; Sergeev, N. S.; Zhilina, Z. V.;
ACCEPTED MANUSCRIPT
Gumenyuk, V. V.; Starikova, Z. A.; Simenel, A. A.; Morozova, N. B.;
Sviridova, I. K.; Babin, V. N. Appl. Organometal. Chem. 2008; 22,
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M. M. Appl. Organometal. Chem. 2009, 23, 219–224; (c) Braga, S. S.;
Silva, A. M. S.; Organometallics 2013, 32, 5626–5639; (d) Rodionov,
A. N.; Zherebker, K. Ya.; Snegur, L. V.; Korlyukov, A. A.; Arhipov,
D. E.; Peregudov, A. S.; Ilyin, M. M.; Ilyin, M. M. Jr.; Nikitin, O. M.;
Morozova, N. B.; Simenel, A. A. J. Organomet. Chem. 2015, 783, 83-
91.
= 0.60 (hexane/Et2O, 1:1). FT-IR (KBr): ṽ = 3083, 1103, 1000,
1
810, 481 (Fc), 734 (P-C), 493 (P=Se), 471 (P-Se) cm-1. H NMR
(400.13 MHz, CDCl3): δ = 2.47 (dt, 2J = 8.8 Hz, 3J = 8.6 Hz, 4 H,
PCH2), 2.80-3.02 (m, 4 H, PhCH2), 4.03, 4.07 (2s, each 1 H, Hα
in Fc), 4.11 (s, 2 H, Hβ in Fc), 4.15 (s, 5 H, C5H5), 4.29 (s, 2 H,
SeCH2), 7.10-7.26 (m, 10 H, Ph). 13C NMR (100.62 MHz,
CDCl3): δ = 30.2 (d, 2J = 2.6 Hz, СH2Ph), 31.7 (SeCH2), 39.1 (d,
1J = 36.0 Hz, PCH2), 68.5 (Cα in Fc), 69.0 (C5H5), 69.2 (Cβ in
Fc), 85.1 (Ci in Fc), 126.5 (p-C in Ph), 128.3 (o-C in Ph), 128.6
(m-C in Ph), 140.2 (d, 3J = 17.3 Hz, i-C in Ph). 31P NMR (161.98
10. (a) Roux, C.; Biot, C. Future Med. Chem. 2012, 4, 783–797; (b) Salas,
P. F.; Herrmann, C.; Orvig, C. Chem. Rev. 2013, 113, 3450–3492.
11. García-Barrantes, P. M.; Lamoureux, G. V.; Pérez, A. L.; García-
Sánchez, R. N.; Martínez, A. R.; San Feliciano, A. Eur. J. Med. Chem.
2013, 70, 548-557.
12. Maguene, G. M.; Jakhlal, J.; Ladyman, M.; Vallin, A.;
Ralambomanana, D. A.; Bousquet, T.; Maugein, J.; Lebibi, J.; Pélinski,
L. Eur. J. Med. Chem. 2011, 46, 31-38.
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1
1
MHz, CDCl3): δ = 48.58 (satellites: JP=Se = 742 Hz, JP-Se = 358
Hz). Anal. Calcd. for C27H29FePSe2 (598.26): C, 54.21; H, 4.89;
Fe, 9.33; P, 5.18. Found: C, 54.50; H, 4.62; Fe, 9.44; P, 5.23.
Acknowledgments
Authors would like to acknowledge the Multi-Access
Chemical Service Center SB RAS for XRD measurements. The
authors are also grateful to the Baikal Analytical Center for
spectral measurements.
15. Zheng, Y.; Wang, C.; Li, C.; Qiao, J.; Zhang, F.; Huang, M.; Ren, W.;
Dong, C.; Huang, J.; Zhou, H.-B. Org. Biomol. Chem. 2012, 10, 9689–
9699.
16. Lillethorup, M.; Torbensen, K.; Ceccato, M.; Pedersen, S. U.;
Daasbjerg, K. Langmuir 2013, 29, 13595−13604.
Supplementary Material
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Fairlamb, I. J. S.; Lynam, J. M.), 2008, pp. 58–73; (b) Taylor, A. W.;
Licence, P. ChemPhysChem 2012, 13, 1917–1926.
Supplementary data for this article can be found in the online
version, at http://dx.doi.org/10.1016/j.tet.... .
18. (a) Lorenzo, A.; Aller, E.; Molina, P. Tetrahedron 2009, 65, 1397–
1401; (b) Sun, R.; Wang, L.; Yu, H.; Abdin, Z.; Chen, Y.; Huang, J.;
Tong, R. Organometallics 2014, 33, 4560–4573.
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