Aluminacyclopentanes in the synthesis of 3-substituted phospholanes and α,ω-bisphospholanes

Article abstract of DOI:10.3762/bjoc.12.43

An efficient one-pot process for the synthesis of 3-substituted phospholanes and α,ω-bisphospholanes was developed. The method involves the replacement of aluminium in aluminacyclopentanes, prepared in situ by catalytic cycloalumination of α-olefins and α,ω-diolefins, by phosphorus atoms on treatment with dichlorophosphines (R'PCl2). Hydrogen peroxide oxidation and treatment with S8 of the synthesized phospholanes and α,ω-bisphospholanes afforded the corresponding 3-alkyl(aryl)-1-alkyl(phenyl)phospholane 1-oxides, 3-alkyl(aryl)-1-alkyl(phenyl)phospholane 1-sulfides, bisphospholane 1,1'-dioxides, and bisphospholane 1,1'- disulfides in nearly quantitative yields. The complexes LMo(CO)5 (L = 3-hexyl-1-phenylphospholane, 3-benzyl-1-methylphospholane, 1,2-bis(1-phenylphospholan-3-yl)ethane, and 1,6-bis(1-phenylphospholan-3-yl)hexane were prepared by the reaction of 3-substituted phospholanes and α,ω-bisphospholanes with molybdenum hexacarbonyl. The structure of the complexes was proved by multinuclear ¹H, ¹³C, and ³¹P spectroscopy.

Full text of DOI:10.3762/bjoc.12.43

Aluminacyclopentanes in the synthesis of 3-substituted
phospholanes and α,ω-bisphospholanes
Vladimir A. D’yakonov*, Alevtina L. Makhamatkhanova, Rina A. Agliullina,
Leisan K. Dilmukhametova, Tat’yana V. Tyumkina and Usein M. Dzhemilev
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2016, 12, 406–412.
Institute of Petrochemistry and Catalysis of Russian Academy of
Sciences, Prospekt Oktyabrya, Ufa 450075, Russian Federation
doi:10.3762/bjoc.12.43
Received: 14 December 2015
Accepted: 12 February 2016
Published: 02 March 2016
Email:
Vladimir A. D’yakonov* - DyakonovVA@gmail.com
* Corresponding author
Associate Editor: J. P. Wolfe
Keywords:
© 2016 D’yakonov et al; licensee Beilstein-Institut.
License and terms: see end of document.
aluminacyclopentanes; Dzhemilev reaction; molybdenum complexes;
phospholanes; zirconium complexes
Abstract
An efficient one-pot process for the synthesis of 3-substituted phospholanes and α,ω-bisphospholanes was developed. The method
involves the replacement of aluminium in aluminacyclopentanes, prepared in situ by catalytic cycloalumination of α-olefins and
α,ω-diolefins, by phosphorus atoms on treatment with dichlorophosphines (R′PCl2). Hydrogen peroxide oxidation and treatment
with S8 of the synthesized phospholanes and α,ω-bisphospholanes afforded the corresponding 3-alkyl(aryl)-1-alkyl(phenyl)phos-
pholane 1-oxides, 3-alkyl(aryl)-1-alkyl(phenyl)phospholane 1-sulfides, bisphospholane 1,1'-dioxides, and bisphospholane 1,1'-
disulfides in nearly quantitative yields. The complexes LMo(CO)5 (L = 3-hexyl-1-phenylphospholane, 3-benzyl-1-methylphospho-
lane, 1,2-bis(1-phenylphospholan-3-yl)ethane, and 1,6-bis(1-phenylphospholan-3-yl)hexane were prepared by the reaction of
3-substituted phospholanes and α,ω-bisphospholanes with molybdenum hexacarbonyl. The structure of the complexes was proved
by multinuclear 1H, 13C, and 31P spectroscopy.
Introduction
A widely used approach for the synthesis of cyclic organophos- This approach was used to obtain materials for light-emitting
phorus compounds (OPC) is the direct transformation of five- diodes (LEDs) [8], phosphorus-containing polymers [9,10],
membered metallacarbocycles based on transition metals to bisphospholes [11], bicyclodiphospholanes and spirobicyclodi-
phosphacarbocycles on treatment with phosphorus dihalides. phospholanes [12,13]. However, this method is faced with some
For example, a method for the direct conversion of zircona- practical complications related to the synthesis of the initial
cyclopentenes [1-4] and zirconacyclopentadienes [5] to substi- zirconacarbocycles: the reactions proceed at low temperatures
tuted phospholenes [6] and phospholes [7] has been reported. (−78 °С) consuming stoichiometric amounts of expensive
406

Beilstein J. Org. Chem. 2016, 12, 406–412.
Cp2ZrCl2. In our opinion, the synthesis of cyclic OPC via cata- The present paper reports the results of experimental studies
lytic cyclometallation reactions that we developed previously that further develop the earlier investigation about the substitu-
[14-17] would be free from the above-indicated drawbacks.
tion of phosphorus atoms for the Al atoms in aluminacyclopen-
tanes with the goal to develop a preparative method for the syn-
Furthermore, analysis of world literature demonstrated that the thesis of five-membered cyclic organophosphorus compounds.
data on direct transformation of aluminacarbocycles [18] to
cyclic OPCs are scarce, except for paper [19] in which this ap- Results and Discussion
proach is implemented for simple olefins. Meanwhile, in our First, we studied the effect of the structure of substituent in po-
opinion, the development of these reactions would give rise to sition 3 of the initial aluminacyclopentanes on the yield of
practically promising one-pot methods for the preparation of a target phospholanes. Under the selected conditions (toluene,
broad range of cyclic and acyclic organophosphorus com- 20–22 °С, 30 min), 3-alkyl-substituted aluminacyclopentanes
pounds of specified structure (phospholanes, phospholenes, 1a–c react with phenyldichlorophosphine to give 3-butyl-1-
phospholes and 1,2- and 1,4-diphosphorus compounds) that phenylphospholane (2a), 3-hexyl-1-phenylphospholane (2b), or
were difficult to synthesize or unknown before. In order to fill 3-octyl-1-phenylphospholane (2c) in ca. 92, 91, and 87% yields,
this gap and to extend the scope of applicability of the catalytic respectively (Scheme 2, Table 1). The isolated organophos-
cycloalumination of unsaturated compounds, we continued phorus compounds 2a–с are 3:2 mixtures of diastereomers
studies along this line, which form the subject of this paper. formed due to the presence of two asymmetric centres in the
molecule at С-3 and P-1. The latter exists due to the high barrier
Previously [19], it was shown for allylbenzene, hex-1-ene, and for inversion of configuration at the phosphorus atom [20].
oct-1-ene that aluminacyclopentanes, prepared by the reaction
of these alkenes with Et3Al in the presence of 5 mol %
Cp2ZrCl2 (20 °С, 6–8 h), react in situ with RPCl2 (R = Me, Ph)
in toluene for 30 min with replacement of the Al atom by a P
atom to give the respective phospholanes in 79–84% yields
(Scheme 1).
Scheme 2: Synthesis of 3-substituted phospholanes.
The diastereomeric mixture was identified by multinuclear 1H,
13C, and 31P NMR spectroscopy and conventionally designated
as the syn and anti isomers in which, for example, the high-
priority substituents at Р-1 and С-3 are proximate in the syn
isomer. Using the homo- and heteronuclear 2D NMR spectro-
Scheme 1: Synthesis of 3-substituted phospholanes according to
earlier data [14-17].
scopy (H,H-COSY, HSQC, HMBC), parameters of the NMR
spectra of some compounds 2 were determined and proved to
Table 1: Results of 3-substituted phospholanes a.
Entry
R
R'
Product
Yield (%)
trans/cis
1
2
3
4
5
6
7
8
Bu
Ph
Ph
Ph
Ph
Ph
Ph
Me
Bu
2ab
2b
92
91
87
93
90
82
84
86
3/2
3/2
3/2
3/2
3/2
3/2
2/1
2/1
Hex
Oct
2c
cyclohexyl
2d
cyclohexen-3-yl
2e
Bn
Bn
Bn
2fb
2gb
2h
aReaction conditions: (i) 10 mmol Et3Al, 5 mol % Cp2ZrCl2, toluene (25 mL), room temperature, 12 hours; (ii) 10 mmol R’PCl2, −5 °C to room temper-
ature, 30 minutes. bThe cyclic OPCs have been previously synthesized and described in [19].
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Beilstein J. Org. Chem. 2016, 12, 406–412.
agree with published data [19]. Specifically, 1-phenyl-3-substi- In the 31Р NMR spectra of phospholane oxides 3a–h and phos-
tuted phospholanes typically show 31Р NMR signals in area of pholane sulfides 4a–h, the phosphorus signal shifts downfield
−14 to −13 ppm, except for the 1-alkyl-3-benzylphospholane 2g to ca. 57–70 ppm relative to the initial phospholanes, and the
and 2h isomers, for which the signals occur at δP = −34 ppm heteronuclear constants 1J(31P13C2) and 1J(31P13C5) observed
and −35 ppm, and −22 to −23 ppm, respectively. The presence in the 13С NMR spectra increase to ca. 53–66 Hz.
of a magnetically active phosphorus atom in the five-mem-
bered heterocycle induces the doublet splitting of the carbon When styrene or 2-vinylnaphthalene reacts with AlEt3 in the
signals in the 13С NMR spectra of 2a–h for both the P-substitu- presence of Cp2ZrCl2, apart from 3-phenyl(naphthyl)-1-ethyl-
ent and the ring. The highest heteronuclear constants J(31P13C) aluminacyclopentanes 5a–f, the reaction mixture contains
for the ring, 1JPC ≈ 10–20 Hz, are found for the α-carbon atoms 2-phenyl(naphthyl)-1-ethylaluminacyclopentane 6a–f [21].
(С-2 and С-5) of phospholanes 2a–h.
Both regioisomers react in situ with phosphorus dihalides and
hydrogen peroxide to afford 1-phenyl(alkyl)-2-arylphospholane
Allylbenzene reacts with AlEt3 (5 mol % Cp2ZrCl2, 20 °С, oxides 7a–f and 1-phenyl(alkyl)-3-arylphospholane oxides 8a–f
12 h) to give 3-benzyl-1-ethylaluminacyclopentane 1f, which in 2:1 ratio in a 69–87% total yield (Table 2). The regioisomers
then reacts with phenyldichlorophosphine giving rise to were isolated by column chromatography (hexane/ethyl acetate/
3-benzyl-1-phenylphospholane 2f in a yield of 82% (Scheme 2). methanol = 5:3:1) and characterized in a separate fraction
(Scheme 4).
When PhPCl2 is replaced by MePCl2 or BuPCl2, the reaction
with 3-benzyl-1-ethylaluminacyclopentane 1f affords the corre-
Table 2: Results of 3-substituted and 2-substituted phospholanes.
sponding phospholanes 2g,h with one of the isomers predomi-
nating (Table 1).
Entry
Ar
R'
Product Ratio
Yield (%)
1
2
3
4
5
6
Ph
Me
Bu
7a, 8a
7b, 8b
7c, 8c
7d, 8d
7e, 8e
7f, 8f
2/1
2/1
2/1
2/1
2/1
2/1
84
87
81
75
72
69
In the case of 3-cyclohexyl- and 3-(сyclohex-3-en-1-yl)-1-
phenylphospholanes (2d and 2e), the number of stereoisomers
increases owing to the additional asymmetric centre С(1′) in the
substituent, and the total yield of these compounds is 90–93%.
Ph
Ph
t-Bu
Ph
Ph
Naphtyl
Naphtyl
Me
Ph
Phospholanes 2а–h readily react with H2O2 in chloroform,
owing to the presence of a lone electron pair at phosphorus to
give phospholane 1-oxides 3а–h in quantitative yields. The
reaction of 2а–h with S8 affords phospholane 1-sulfides 4а–h It should be noted that the phosphorus signals of major intensi-
also in quantitative yields (Scheme 3).
ty of 2-aryl phospholane oxides 8a, 8b, 8d, 8e, 8f, correspond-
ing to one of the stereoisomers, are shifted upfield by
ca. 5–7 ppm with respect to those of 3-aryl-substituted phospho-
lane oxides 7. In contrast, the 31P NMR signal of the second
isomer of 8 is shifted to lower field.
For further development of this study, it appeared pertinent to
apply our method in the preparation of α,ω-bisphospholane
compounds by the reaction of phosphorus dihalides with bisalu-
minacyclopentanes (Scheme 5).
Scheme 3: Synthesis of 3-substituted phospholane oxides and
sulfides.
Scheme 4: Synthesis of 3-substituted 7a–f and 2-substituted 8a–f phospholanes.
408

Beilstein J. Org. Chem. 2016, 12, 406–412.
Organophosphorus compounds, including cyclic ones, are
known to readily form complexes with transition metals, which
are extensively studied and used in homogeneous catalytic reac-
tions. Therefore, in order to study the properties of the cyclic
OPC that we prepared and to demonstrate how they could be
used as ligands, we investigated the reaction of 3-substituted
phospholanes and bisphospholanes with Mo(CO)6, resulting in
the preparation of molybdenum complexes. For example,
3-hexyl-1-phenylphospholane and 3-benzyl-1-methylphospho-
lane react with Mo(CO)6 furnishing molybdenum complexes
13b and 14g (Scheme 7).
Scheme 5: Synthesis of bisphospholanes.
Thus bisaluminacyclopentane 9a, synthesized by catalytic
cycloalumination of 1,7-octadiene, was subjected without isola-
tion to the substitution reaction with aryl(alkyl)dichlorophos-
phine with replacement of Al by Р (ca. 20 °С, 30 min) to give
bisphospholane 10a as a mixture of isomers in a total yield of
84–85%.
Scheme 7: Synthesis of the molybdenum complex (3-hexyl(benzyl)-1-
phenyl(methyl)phospholane)Mo(CO)5.
Under the selected conditions, bisaluminacyclopentanes 9b–e,
prepared by catalytic cycloalumination of 1,5-hexadiene and
1,9-decadiene, react with phenyl(methyl, butyl)dichlorophos-
phine to give 1,2-bis(1-phenylphospholan-3-yl)ethane (10b),
1,2-bis(1-butylphospholan-3-yl)ethane (10d), 1,4-bis(1-
methylphospholan-3-yl)butane (10e), and 1,6-bis(1-phenylphos-
pholan-3-yl)hexane (10с) in 85 % yields.
The complex formation is evidenced by changes in the NMR
spectral parameters of compounds 13b and 14g in relation to the
initial phospholanes. A typical feature is the downfield shift of
the 31Р NMR signals. As a result, both compounds were found
to exhibit close chemical shifts δP ≈ 25 ppm and δP ≈ 26 ppm
for the diastereomers formed, irrespective of the nature of sub-
stituent R', which is indicative of equal pyramidality of the
bonds of the phosphorus atom incorporated in the molybdenum
complex. In addition, the С-5 signal in the 13С NMR spectra is
shifted downfield by ca. 8 ppm and the constant JPC5 = 24.1 Hz
(for example, for 13b) is much higher not only compared to the
corresponding atom in the initial phospholane 2b but also than
JPC2 = 3.0 Hz in compound 13b. In view of the fact that the
phosphorus–carbon constants obey the Karplus equation [22],
this result suggests that the conformation of the five-membered
heterocycle changes upon the formation of the complex with
molybdenum hexacarbonyl. Similarly, bisphospholanes 10a and
10c react with Mo(CO)6 to form molybdenum complexes 15a
and 16c (Scheme 8). The resulting molybdenum complexes are
oily liquids. The structure of the complexes was also proved by
spectral data.
Similarly to phospholanes 2a–h, the resulting bisphospholanes
10a–c readily react with H2O2 in chloroform or with elemental
sulfur to furnish the corresponding bisphospholane 1,1'-diox-
ides 11a–c and bisphospholane 1,1'-disulfides 12a–c
(Scheme 6).
Scheme 6: Synthesis of bisphospholane-1,1'-oxides and bisphospho-
lane-1,1'-sulfides.
Diastereomeric cleavage of signals in the 13С NMR spectra of
bisphospholanes observed only for compounds 10а, 10d, 11а,
12а in which the phospholane moieties are linked by two meth-
ylene groups, obviously as a result of mutual influence of the
proximate asymmetric centres at C-3 and С-3′. Ratios of stereo-
isomers were determined by HPLC method as 2:1 (see Support-
ing Information File 2, Figure S1).
Scheme 8: Synthesis of molybdenum complexes (1,2(1,6)-bis(1-
phenylphospholan-3-yl)ethane(hexane))Mo(CO)5.
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Beilstein J. Org. Chem. 2016, 12, 406–412.
Conclusion
130.07 (JPC = 16.1 Hz, C(7), C(11)), 130.13 (JPC = 15.1 Hz,
Thus, as a continuation of investigations dealing with the search C(7), C(11)), 142.47, 142.84 (JPC = 23.1 Hz, C(6)) (P-Ph); 31P
for effective methods for the synthesis of five-membered cyclic NMR (161.97 MHz, CDCl3) δ −13.5, −13.9; MALDI–TOF: m/z
organophosphorus compounds, we developed a preparative сalcd for C18H30P ([M + H]+): 277.4046; found: 277.4.
process for the one-pot conversion of aluminacyclopentanes,
Preparation of 3-alkyl(aryl)phospholane-1-
obtained in situ by catalytic cycloalumination of olefins or
diolefins with AlEt3, to phospholanes, phospholane oxides or oxides (general procedure)
phospholane sulfides, including bisphospholanes and their de- A 30% solution of hydrogen peroxide (0.7 mL, 6 mmol) was
rivatives in high yields.
slowly added dropwise with vigorous stirring to a solution of
3-alkyl(benzyl)-1-alkyl(phenyl)phospholane (5 mmol), synthe-
The developed methods are distinguished by easy implementa- sized as described above, in chloroform (10 mL) and the mix-
tion of the reaction with the use of accessible reagents and ture was stirred for 1 h. Then the reaction mixture was washed
monomers, which makes them quite promising for the use in with water (3 × 5 mL) and the organic layer was dried with
both the laboratory practice and industry.
MgSO4. The solvent was evaporated and the residue was chro-
matographed on silica gel (hexane/ethyl acetate/methanol
5:3:1). 3-Octyl-1-phenylphospholane-1-oxide (3c) in the mix-
ture in a ratio of 3:2: Calcd for C18H29OP: C, 73.94; H,
10.00%; found: C, 73.7%; H, 9.8%; 1H NMR (400.13 MHz,
CDCl3) δ 0.81 (t, 3J = 7.2 Hz, 6H, C(8')H), 1.17–1.60 (m, 30H,
C(2)Ha, C(4)Ha, C(1')H, C(2')H, C(3')H, C(4')H, C(5')H,
C(6')H, C(7')H), 1.70 (m, 1H, C(2)Ha), 1.80 (m, 1H, C(4)Ha),
1.87 (m, 1H, C(5)Ha), 1.94–2.12 (m, 2H, C(3)H, C(5)Ha),
2.14–2.35 (m, 7H, C(2)Hb, C(3)H, C(4)Hb, C(5)Hb), 7.36–7.56,
7.60–7.78 (m, 10H, Ph); 13C NMR (100.62 MHz, CDCl3) δ
13.82 (C(8')), 22.35 (C(7')), 27.51, 27.60 (C(2')), 28.94, 28.96
(C(4')), 29.19 (JPC = 66.4 Hz, C(5)), 29.21 (C(5')), 29.32, 29.36
(C(3')), 30.18 (JPC = 66.4 Hz, C(5)), 30.99 (JPC = 6.0 Hz, C(4)),
31.55 (C(6')), 31.93 (JPC = 7.0 Hz, C(4)), 35.87 (JPC = 55.3 Hz,
C(2)), 35.99 (JPC = 12.1 Hz, C(1')), 36.04 (JPC = 14.1 Hz,
C(1')), 36.16 (JPC = 53.3 Hz, C(2)), 38.60, 40.21 (JPC = 8.0 Hz,
C(3)), 128.39 (JPC = 12.1 Hz, C(8), C(10)), 129.55 (JPC = 10.1
Hz, C(7), C(11)), 131.40 (JPC = 3.0 Hz, C(9)), 133.90 (JPC =
Experimental
Preparation of 3-alkyl(aryl)phospholanes
(general procedure)
A glass reactor maintained under dry argon at 0 °C was succes-
sively charged, with stirring, with toluene (25 mL), Cp2ZrCl2
(0.298 g, 1 mmol), olefin (10 mmol), and AlEt3 (1.8 mL,
10 mmol) The mixture was warmed up to room temperature
(ca. 20 °C) and stirred for 12 h. Then the reaction mixture was
cooled down to −5 to −10 °С, alkyl(phenyl)dichlorophosphine
(10 mmol) was added dropwise, and the mixture was stirred at
room temperature for additional 30 min. Then the reaction mix-
ture was treated with a saturated aqueous solution of NH4Cl and
the reaction products were extracted with diethyl ether and
dried with MgSO4. The solvent was evaporated and the target
phospholanes were isolated by vacuum distillation. All opera-
tions were carried out in an argon flow.
The general procedure and analytical data for compounds 2a, 89.5 Hz, C(6)), 134.00 (JPC = 90.5 Hz, C(6)) (P-Ph); 31P NMR
2b, 2f. 2g and 3a, 3b, 3f, 3g were previously described in [19]. (161.97 MHz, CDCl3) δ 59.7, 59.4; MALDI TOF: m/z calcu-
lated for C18H30OP ([M+ H]+): 293.4040; found: 293.5.
3-Octyl-1-phenylphospholane (2c) in the mixture in a ratio of
General procedure for the preparation of
3:2: Colorless oil (87%); bp 215–218 °C (9 torr); calcd for
C18H29P: C, 78.22%; H, 10.58%; found: C, 78.3%; H, 10.6%; 3-alkyl(aryl)phospholane-1-sulfides
1H NMR (400.13 MHz, CDCl3) δ 0.95 (t, 3J = 6.8 Hz, 6H, Reactions were performed under argon. Sulfur (0.13 g, 4 mmol)
C(8')H), 1.27–1.63 (m, 32H, C(1')H, C(2')H, C(3')H, C(4')H, was added with cooling to a solution of 3-alkyl(aryl)phospho-
C(5')H, C(6′)H, C(7′))H, C(4)Ha, C(2)Ha), 1.94–2.03 (m, 4H, lane (4 mmol) (prepared as described above) in 10 mL toluene,
C(3)H, C(5)Ha), 2.10–2.20 (m, 4H, C(2)Hb, C(4)Hb), 2.26 (m, and the mixture was stirred for 4 h. After filtration through a
2H, C(5)Hb), 7.24–7.30, 7.32–7.38, 7.42–7.48 (m, 10H, Ph); thin layer of silica gel the solvent was evaporated to give a
13C NMR (100.62 MHz, CDCl3) δ 14.15 (C(8')), 22.70 (C(7')), colorless oil. 3-Hexyl-1-phenylphospholane-1-sulfide (4b) in
25.79 (JPC = 12.1 Hz, C(5)), 26.60 (JPC = 10.1 Hz, C(5)), the mixture in a ratio of 3:2: Calculated for C16H25PS: C,
28.49, 28.61 (C(2')), 29.04, 29.05 (C(4')), 29.32 (C(5')), 29.57, 68.53%; H, 8.99%; found: C, 68.4%; H, 8.0%; 1H NMR
29.64 (C(3')), 31.63 (C(6')), 32.92 (JPC = 13.1 Hz, C(2)), 33.16 (400.13 MHz, CDCl3) δ 0.91 (t, 3J = 6.8 Hz, 6H, C(6')H),
(JPC = 11.1 Hz, C(2)), 33.95 (JPC = 3.0 Hz, C(4)), 34.24 (JPC = 1.25–1.43 (m, 16H, C(2')H, C(3')H, C(4')H, C(5')H), 1.43–1.61
4.0 Hz, C(4)), 35.60 (JPC = 3.0 Hz, C(1')), 35.86 (JPC = 5.0 Hz, (m, 5H, C(1')H, C(4)Ha), 1.83–1.95 (m, 2H, C(2)Ha, C(4)Hа),
C(1')), 41.82 (JPC = 4.0 Hz, C(3)), 43.02 (JPC = 1.0 Hz, C(3)), 1.99 (m, 1H, C(2)Ha), 2.11–2.52 (m, 8H, C(2)Hb, C(3)H,
126.87 (C(9)), 127.90, 127.91 (JPC = 5.0 Hz, C(8), C(10)), C(4)Hb, C(5)Ha, C(5)Hb), 2.60 (m, 1H, C(5)Hb), 2.66 (m, 1H,
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Beilstein J. Org. Chem. 2016, 12, 406–412.
C(2)Hb), 7.42–7.53, 7.82–7.94 (m, 10H, Ph); 13C NMR (100.62 by silica gel column chromatography (hexane) giving a dark
MHz, CDCl3) δ 13.77 (C(6')), 22.27, 22.29 (C(5')), 27.62, 27.68 brown, thick liquid. 1,2-Bis(1-pentacarbonylmolybdenum-1-
(C(2')), 29.00 (C(3')), 31.41, 31.43 (C(4')), 31.86 (JPC = 6.0 Hz, phenylphospholan-3-yl)ethane (15a) as a mixture of isomers.
C(4)), 33.62 (JPC = 4.0 Hz, C(4)), 35.44 (JPC = 14.1 Hz, C(1')), Calcd for C32H28Mo2O10P2: C, 46.51%; H, 3.42%; found: C,
35.64 (JPC = 53.3 Hz, C(5)), 35.71 (JPC = 12.1 Hz, C(1')), 36.49 46.5%; H, 3.5%; 1H NMR (400.13 MHz, CDCl3) δ 1.28–1.39
(JPC = 53.3 Hz, C(5)), 39.74 (JPC = 8.0 Hz, C(3)), 41.78 (JPC = (m, 2H, C(4)Ha, C(4)Hb), 1.40–1.60 (m, 2H, C(4)Ha, C(4)Hb),
6.0 Hz, C(3)), 41.94 (JPC = 54.3 Hz, С(2)), 42.38 (JPC = 53.3 1.64–1.73 (m, 1H, C(2)Ha), 1.84–1.94 (m, 1H, C(3)H),
Hz, C(2)), 128.30 (JPC = 12.1 Hz, C(8), C(10)), 130.00 (JPC = 1.98–2.22 (m, 6H, C(6′), C(2)Hb, C(3)H), 2.35–2.58 (m, 3H,
11.1 Hz, C(7), C(11)), 131.07 (JPC = 2.0 Hz, C(9)), 133.76, C(5)Ha, C(5)Hb, C(2)Ha), 2.60–2.70 (m, 3H, C(5)Ha, C(5)Hb,
133.84 (JPC = 70.4 Hz, C(6)) (P-Ph); 31P NMR (161.97 MHz, С(2)Hb), 7.34–7.56 (m, 10H, P-Ph); 13C NMR (100.62 MHz,
CDCl3) δ 57.72; MALDI TOF: m/z сalculated for C16H26PS CDCl3) δ 31.29, 31.35 (JPC = 23.1 Hz, C(5)), 32.01 (JPC = 23.1
([M + H]+): 281.4174; found: 281.3.
Hz, C(5)), 32.05 (JPC = 24.1 Hz, C(5)), 33.35, 33.40, 34.13,
34.17, 34.22 (С(4)), 34.37, 34.44, 34.52, 34.59 (C(6')), 38.31,
38.35, 38.37 (JPC = 23.1 Hz, C(2)), 38.50, 38.54 (C(2)), 41.74,
41.82, 41.91, 42.36, 42.42 (C(3)), 128.84, 128.94, 129.03,
General procedure for the preparation of Mo
complexes 13b, 14g
Reactions was performed under argon using standard Schlenk 129.19, 139.44, 140.11 (JPC = 28.2 Hz, C(6)) (Р-Ph), 205.74,
techniques. A mixture of Mo(CO)6 (0.79 g, 3 mmol) and 205.83 (COcis), 210.49, 210.55 (JPC = 22.1 Hz, COtrans); 31P
3-hexyl(benzyl)-1-phenyl(methyl)phospholane 2b, 2g (3 mmol) NMR (161.97 MHz, CDCl3) δ 25.3, 26.3.
was stirred under reflux in 15 mL THF for 24 h. The colorless
solution became dark-brown during this time. The solvent was
Supporting Information
removed under vacuum and the residue was chromatographed
on silica gel (hexane). The product was obtained as dark green
Detailed synthesis and characterization procedures are
thick liquid. (3-Hexyl-1-phenylphospholane)pentacarbonyl-
provided for all compounds synthesized and characterized.
molybdenum (13b) in the mixture in a ratio of 1:1: Calcd for
NMR spectra are provided for all compounds for which
C21H25MoO5P: C, 52.08%; H, 5.20%; found: C, 52.2%; H,
NMR data are reported.
5.3%; 1H NMR (400.13 MHz, CDCl3) δ 0.20–1.01 (s, 6H,
Supporting Information File 1
C(6′)H), 1.30–1.56 (s, 20H, C(5′)H, C(3′)H, C(2′)H, C(4′)H,
C(1′)H), 1.58–1.64 (m, 2H, C(4)H), 1.72–1.82 (m, 1H, C(2)Ha),
1.93–2.02 (m, 1H, C(3)H), 2.06–2.27 (m, 4H, C(4)Hb, C(2)Hb,
C(3)H), 2.41–2.57 (m, 3H, C(5)Ha, C(5)Hb), 2.58–2.80 (m, 3Н,
С(5)Hb, С(2)Ha, С(2)Hb), 7.23–7.26, 7.31–7.33, 7.37–7.44,
7.45–7.56 (m, 10Н, Ph); 13C NMR (100.62 MHz, CDCl3) δ
14.10 (C(6')), 22.66, 22.72 (C(5')), 28.39, 28.42 (C(3')), 29.37,
29.44 (C(2')), 31.45 (JPC = 22.1 Hz, C(5)), 31.81 (C(4')), 32.16
(JPC = 24.1 Hz, C(5)), 33.42, 34.13 (C(4)), 35.70 (JPC = 8.0 Hz,
C(1')), 35.75 (JPC = 9.1 Hz, C(1')), 38.19 (C(2)), 38.41 (JPC =
3.0 Hz, C(2)), 41.78 (JPC = 1.0 Hz, C(3)), 42.30 (C(3)), 128.81,
Experimental details, characterization data of all products.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-12-43-S1.pdf]
Supporting Information File 2
NMR spectra.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-12-43-S2.pdf]
128.88 (JPC = 10.1 Hz), 128.95 (JPC = 11.1 Hz), 129.08, 139.67 Acknowledgements
(JPC = 27.2 Hz, C(6)), 140.24 (JPC = 28.2 Hz, C(6)) (P-Ph), This work was supported financially by the Russian Founda-
205.75 (JPC = 9.1 Hz, COcis), 205.77 (JPC = 9.1 Hz, COcis), tion for Basic Research (Grants 15-33-20043, 16-33-00193).
210.51 (JPC = 22.1 Hz, COtrans), 210.57 (JPC = 21.1 Hz, The HPLC analysis was performed with equipment at the
COtrans); 31P NMR (161.97 MHz, CDCl3): δ 26.00, 25.20. Center for the Сollective Use “Chemistry” of the Ufa Institute
of Chemistry of the Russian Academy of Sciences.
General procedure for the preparation of Mo
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