Synthesis and transformations of metallacycles 46. Catalytic cycloalumination reaction in the synthesis of bis(phospholanes)

Article abstract of DOI:10.1007/s11172-015-1182-1

An efficient one-pot synthesis of bis(phospholanes) was elaborated, which included a sequential Cp₂ZrCl₂-catalyzed cycloalumination of α,ω-diolefins with AlEt₃, giving the corresponding bis(aluminacyclopentanes), and their in situ reaction with dihalophosphines to furnish the target α,ω-bis(phospholanes). The reaction of these compounds with H₂O₂ or elementary sulfur gave the corresponding bis(phospholane 1-oxides) and bis(phospholane 1-sulfides).

Full text of DOI:10.1007/s11172-015-1182-1

Russian Chemical Bulletin, International Edition, Vol. 64, No. 10, pp. 2493—2497, October, 2015
2493
Synthesis and transformations of metallacycles
46.* Catalytic cycloalumination reaction
in the synthesis of bis(phospholanes)
V. A. D´yakonov, A. L. Makhamatkhanova, R. A. Agliullina, T. V. Tyumkina, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347) 284 2750. Eꢀmail: DyakonovVA@rambler.ru
An efficient oneꢀpot synthesis of bis(phospholanes) was elaborated, which included
a sequential Cp2ZrCl2ꢀcatalyzed cycloalumination of α,ωꢀdiolefins with AlEt3, giving the
corresponding bis(aluminacyclopentanes), and their in situ reaction with dihalophosphines to
furnish the target α,ωꢀbis(phospholanes). The reaction of these compounds with H2O2
or elementary sulfur gave the corresponding bis(phospholane 1ꢀoxides) and bis(phospholane
1ꢀsulfides).
Key words: cycloalumination, organoaluminum compounds, α,ωꢀdiolefins,
dichlorophosphines, phospholanes, heterocycles, metal complex catalysis, zirconium
complexes.
Scheme 1
Bidentate organophosphorus ligands are regarded as
occupying a special place in organic synthesis and metal
complex catalysis. Nowadays, several hundred of highly
efficient catalyst systems based on bis(phospholanes) such
as BPE,2 BINAP,3 dppe,4 BisP*,5 DIOP6 are used in
everyday practice of organic synthesis, and the number
of new catalysts on their basis is steadily growing. Apart
from that, among the phosphorusꢀcontaining bidentate
ligands the share of compounds containing phospholane
structural fragments, for example, the ligands of DuPhos7
and TangPhos family,8 is constantly increasing.
In order to develop approaches to the synthesis
of organophosphorus ligands containing two phospholane
fragments in the structure, we suggested an idea of
a possibility to use for this purpose a catalytic cycloꢀ
alumination reaction9 of α,ωꢀdienes, as well as a developed
by us conditions for the replacement of Al atoms in
aluminacyclopentanes with P atoms using RPCl2.
Earlier,10 we have shown that the in situ reaction of
simple aluminacyclopentanes 1, obtained by the reaction
of terminal alkenes with Et3Al in the presence of Cp2ZrCl2
(5 mol.%) at 20 °C over 12 h, with RPCl2 (R = Me, Ph)
in toluene within 30 min leads to the replacement of
aluminum atoms by phosphorus atoms with the formation
of the corresponding phospholanes 2 in 79—84% yield
(Scheme 1).
[Zr] = Cp2ZrCl2; R = Bn, nꢀBu, nꢀHex; R´ = Me, Ph
important to confirm a possibility to extend this
method to the synthesis of α,ωꢀbisꢀphospholane
compounds by the reaction of dihalophosphines with bisꢀ
aluminacyclopentanes obtained in situ by the Zrꢀcatalyzed
cycloalumination of α,ωꢀdienes using Et3Al.
As a first step, we studied a Cp2ZrCl2ꢀcatalyzed
cycloalumination of α,ωꢀdiolefins upon treatment with
Et3Al. It was found that under these conditions
1,7ꢀoctadiene reacted with a twoꢀfold excess of Et3Al
in the presence of 10 mol.% Cp2ZrCl2 (40 °C, 4 h)
without solvent, giving a mixture of monoꢀ and
According to this idea on the synthesis of
organophosphorus bidentate ligands, initially it seemed
* For Part 45, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2494—2497, October, 2015.
1066ꢀ5285/15/6410ꢀ2493 © 2015 Springer Science+Business Media, Inc.

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D´yakonov et al.
Scheme 2
Scheme 3
[Zr] = Cp2ZrCl2
n = 2 (a), 4 (b), 6 (c)
cycloalumination of 1,5ꢀhexadiene and 1,9ꢀdecadiene,
react with phenyldichlorophosphine with the formation
of 3,3´ꢀethaneꢀ1,2ꢀbis(1ꢀphenylphospholane) (7a) and
3,3´ꢀhexaneꢀ1,6ꢀbis(1ꢀphenylphospholane) (7c) in 70 and
77% yield, respectively.
[Zr] = Cp2ZrCl2
n = 2 (a), 4 (b), 6 (c)
To reliably establish the structure of bis(phospholanes)
7a—c, they were involved in the reaction with H2O2 in
chloroform and with elementary sulfur, which resulted
in the formation of bis(phospholane 1ꢀoxides) 8a—c and
bis(phospholane 1ꢀsulfides) 9a,b in quantitative yields
(Scheme 4).
bis(aluminacyclopentanes) (ACP) in 1 : 1 ratio and 89%
total yield (Scheme 2).
When the reaction was carried out in toluene, the
percentage of bis(aluminacyclopentanes) increased by
a
factor of 2, with the ratio of monoꢀ and
bis(aluminacyclopentanes) being 1 : 2, respectively.
An increase in the amount of Et3Al involved in the reaction
also leads to the increase in the percentage of
corresponding bisꢀaluminacyclopentane. Thus, for the
ratio of the reaction components 1,7ꢀoctadiene : [Al] : [Zr]
equal to 1 : 3 : 0.1, in toluene the ratio of monoꢀ and
bis(aluminacyclopentanes) was 1 : 3, when the ratio
1,7ꢀoctadiene : [Al] : [Zr] was changed to 1 : 6 : 0.1, the
content of bis(aluminacyclopentanes) in the reaction
mixture increased to 86%. It was shown that
cycloalumination of 1,5ꢀhexadiene and 1,9ꢀdecadiene
under these conditions (α,ωꢀdiene : [Al] : [Zr] = 1 : 6 : 0.1,
solvent toluene) with subsequent hydrolysis of the reaction
mixture led to the formation of 3,6ꢀdimethyloctane (5a)
and 3,10ꢀdimethylundecane (5c) in 74 and 79% yield,
respectively.
Scheme 4
Further experiments showed that bis(aluminaꢀ
cyclopentane) 3b, obtained by cycloalumination of
1,7ꢀoctadiene using a sixꢀfold excess of Et3Al in the
presence of 10 mol.% Cp2ZrCl2 in toluene, reacted in situ
with phenyldichlorophosphine with the formation of bisꢀ
phospholane 7b as a mixture of cisꢀ and transꢀisomers
(1 : 1) in 76% total yield (Scheme 3).
The structure of new compounds was established
using 1D (1H, 13C, 31P, DEPT 135) and 2D (COSY HH,
HSQC, HMBC) homoꢀ and heteronuclear correlation
NMR spectroscopy. Thus, the phenylꢀsubstituted bisꢀ
Under the conditions described above, bisꢀ
aluminacyclopentanes 3a and 3c, obtained by the catalytic

Catalytic cycloalumination
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 10, October, 2015
2495
standard. The ratio of isomers was determined based on the
signal intensities in the 1H and 13C NMR spectra. Reactions
with organometallic compounds were carried out under dry
argon. Solvents were dried and distilled before use. Phosphines
and Cp2ZrCl2 (Acros) and Et3Al (92%) (SigmaꢀAldrich) were
commercially available.
(phospholanes) are characterized by the localization of
the 31P NMR signals in the region of δ –14—–13. Because
of the presence of a lone pair of electrons (LPE) on the
phosphorus atom, the values of the heteronuclear constants
for αꢀcarbon atoms of the phospholane ring C(2) and C(5)
1
in the 13C NMR spectra of compounds 7a—c are JP,C
≈
Synthesis of bis(phospholanes) (general procedure). Toluene
(20 mL), Cp2ZrCl2 (0.149 g, 0.5 mmol), α,ωꢀdiolefin (5 mmol),
and AlEt3 (5.5 mL, 30 mmol) were sequentially placed into
a glass reactor under dry argon at 0 °C with stirring. The
temperature was raised to 40 °C, and the reaction mixture was
stirred for 4 h and cooled to –5— –10 °C, followed by a dropwise
addition of dichlorophenylphosphine (4.1 mL, 30 mmol) and
stirring at room temperature for another 30 min. Then, the
reaction mixture was treated with saturated aqueous solution of
NH4Cl, the reaction products were extracted with diethyl ether
and dried with MgSO4. The solvent was evaporated, the volatile
fractions were removed by distillation in vacuo. The residue was
dissolved in some toluene, applied to a short layer of silica gel,
and sequentially washed off with hexane and ethyl acetate. The
target product was isolated using a hexane—ethyl acetate—
methanol solvent mixture (5 : 3 : 1). The solvents were
evaporated. All the manipulations were carried out under argon.
3,3´ꢀEthyleneꢀ1,2ꢀbis(1ꢀphenylphospholane) (7a). The yield
was 70%. Found (%): C, 74.34; H, 7.92. C22H28P2. Calculated
(%): C, 74.56; H, 7.96. 1H NMR, δ: 1.23—1.60 (m, 16 H, C(2)Ha,
C(2´)Ha, C(4)Ha, C(4´)Ha, C(6)H2, C(6´)H2); 1.75—1.97 (m, 8 H,
C(3)H, C(3´)H, C(5)Ha, C(5´)Ha); 1.98—2.14 (m, 8 H, C(2)Hb,
C(2´)Hb, C(4)Hb, C(4´)Hb, C(5)Hb, C(5´)Hb); 2.15—2.26
(m, 2H, C(5)Hb, C(5´)Hb); 2.27—2.44 (m, 2H, C(2)Hb,
C(2´)Hb); 7.20—7.26, 7.27—7.35, 7.36—7.44 (all m, 20 H, Ph).
≈ 10—12 Hz, whereas the corresponding values for
bis(phospholane 1ꢀoxides) 8a—c and bis(phospholane
1ꢀsulfides) 9a—b increase to ~66—68 Hz. In the 31P NMR
spectra of bis(phospholane 1ꢀoxides) 8a—c, the chemical
shift for the phosphorus atom was found in the region of
δ ~59, whereas for bis(phospholane 1ꢀsulfides) 9a—b
it was at δ ~57. The spectra of compounds 7a—c, 8a—c,
9a—b exhibit double sets of signals because of the syn,antiꢀ
isomerism at the asymmetric phosphorus atom. The 13C
NMR spectra of compounds 7a, 8a, 9a, in which the
phospholane fragments are bound by two methylene
groups, are distinguished by the multiple splitting of
signals, obviously, attributed to a mutual influence of the
close in space asymmetric centers on the P atoms and
restricted rotation around the C—C methylene bonds
in the bis(phospholanes) under consideration, binding the
phospholane fragments.
In conclusion, we suggested an efficient oneꢀpot
synthesis of poorly available bis(phospholanes). The
elaborated method is based on the replacement of
aluminum atoms in bisꢀaluminacyclopentanes with the
phosphorus atoms, using dichlorophosphines. A possibility
of transformation of bis(phospholanes) to bis(phosphoꢀ
lane 1ꢀoxides) and bis(phospholane 1ꢀsulfides) was
demonstrated. The bis(phospholanes) obtained are of
interest as bidentate ligands in metal complex catalysis,
monomers in the preparation of phosphorusꢀcontaining
macrocycles, as well as potential biologically active
compounds.
13C NMR, δ: 24.11 (C(5), 1JP,C = 12.1 Hz); 26.43 (C(5), 1JP,C
=
1
= 10.1 Hz); 26.43 (C(5), JP,C = 10.1 Hz); 32.77, 32.81, 32.83,
32.85, 32.91, 32.94, 32.96, 32.98, 33.06, 33.10, 33.17, 33.21
(C(2)); 33.81, 33.83, 33.85, 33.88 (C(4)); 34.12, 34.16,34.18,
34.20 (C(4)); 34.56, 34.58, 34.62, 34.66, 34.69, 34.81, 34.83,
34.85, 34.87 (C(6)); 41.89, 41.92, 41.93, 41.97, 42.02 (C(3));
43.07, 43.08, 43.16, 43.17 (C(3)); 126.89 (Ph, JP,C = 2.0 Hz);
3
2
127.91 (Ph, JP,C = 5.0 Hz); 130.00 (Ph, JP,C = 16.1 Hz);
2
130.02 (Ph, JP,C = 16.1 Hz); 142.25 (br, Ph, JP,C = 23.1 Hz);
142.71 (br, Ph, JP,C = 23.1 Hz). 31P NMR, δ: –14.18, –13.56.
3,3´ꢀTetramethyleneꢀ1,4ꢀbis(1ꢀphenylphospholane) (7b). The
yield was 76%. Found (%): C, 75.12; H, 8.40. C24H32P2.
Calculated (%): C, 75.37; H, 8.43. 1H NMR, δ: 1.25—1.42
(m, 20 H, C(4)Ha, C(4´)Ha, C(6)H2, C(6´)H2, C(7)H2,
C(7´)H2); 1.42—1.60 (m, 4 H, C(2)Ha, C(2´)Ha); 1.83—2.01
(m, 8 H, C(3)H, C(3´)H, C(5)Ha, C(5´)Ha); 2.02—2.18 (m, 8 H,
C(2)Hb, C(2´)Hb, C(4)Hb, C(4´)Hb, C(5)Hb, C(5´)Hb); 2.18—
2.30 (m, 2 H, C(5)Hb, C(5´)Hb); 2.33—2.46 (m, 2 H, C(2)Hb,
C(2´)Hb); 7.23—7.28, 7.30—7.36, 7.40—7.47 (all m, 20 H, Ph).
Experimental
Chromatographic analysis was carried out on a Shimadzu
GCꢀ9A instrument, a 2000×2ꢀmm column, stationary phase
silicon SEꢀ30 (5%) on Chromaton NꢀAWꢀHMDS (0.125—0.160
mm), carrier gas helium (30 mL min–1), the temperature was
programmed from 50 to 300 °C at the rate of 8 deg min–1
.
1H, 13C, and 31P NMR spectra were recorded on a Bruker
Avanceꢀ400 spectrometer (100.58 MHz for 13C, 400.00 MHz
for 1H, and 161.92 MHz for 31P) in CDCl3. Mass spectra were
13C NMR, δ: 26.02 (C(5), 1JP,C = 11.1 Hz); 26.82 (C(5), 1JP,C
=
=
= 9.1 Hz); 28.91, 28.95, 29.02, 29.06 (C(7)); 32.81 (C(2), 1JP,C
recorded on
a MALDI TOF/TOF AutoflexꢀIII Bruker
1
= 12.1 Hz); 33.07 (C(2), JP,C = 11.1 Hz); 33.88 (C(4)); 34.19
(C(4), JP,C = 3.0 Hz); 35.43 (C(6), JP,C = 3.0 Hz); 35.72
(C(6), JP,C = 5.0 Hz); 41.67, 41.69, 41.72, 41.74 (C(3)); 42.87
instrument with 2,5ꢀdihydroxybenzoic acid (2,5ꢀDHB) and
αꢀcyanoꢀ4ꢀhydroxycinnamic acids (CHCA) as matrices in the
reflective mode with the registration of positive ions. Elemental
analysis of the samples was carried out on Karlo Erba, model 1106
elemental analyzer. TLC was carried out on Silufol UVꢀ254 plates
in the hexane—ethyl acetate—methanol (5 : 3 : 1) solvent system,
visualizing in the iodine vapors. Acros silica gel (0.060—0.200 mm)
was used for column chromatography. Product yields were
determined using GLC analysis with undecane as an internal
2
3
3
(C(3)); 126.97, 127.94 (Ph, 3JP,C = 5.0 Hz); 130.06 (Ph, 2JP,C
= 16.1 Hz); 130.13 (Ph, 2JP,C = 16.1 Hz); 142.28 (br, Ph, JP,C
=
=
= 23.1 Hz); 142.72 (br, Ph, JP,C = 23.1 Hz). 31P NMR, δ: –13.55,
–13.18.
3,3´ꢀHexamethyleneꢀ1,6ꢀbis(1ꢀphenylphospholane) (7c). The
yield was 77%. Found (%): C, 75.92; H, 8.81. C26H36P2.

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D´yakonov et al.
1
Calculated (%): C, 76.07; H, 8.84. 1H NMR, δ: 1.27—1.47
(m, 28 H, C(4)Ha, C(4´)Ha, C(6)H2, C(6´)H2, C(7)H2, C(7´)H2,
C(8)H2, C(8´)H2); 1.48—1.64 (m, 4 H, C(2)Ha, C(2´)Ha); 1.83—
2.02 (m, 8 H, C(3)H, C(3´)H, C(5)Ha, C(5´)Ha); 2.03—2.21
(m, 8 H, C(2)Hb, C(2´)Hb, C(4)Hb, C(4´)Hb, C(5)Hb, C(5´)Hb);
2.21—2.33 (m, 2 H, C(5)Hb, C(5´)Hb); 2.36—2.50 (m, 2 H,
C(2)Hb, C(2´)Hb); 7.25—7.30, 7.33—7.38, 7.40—7.41, 7.43—
7.49 (all m, 20 H, Ph). 13C NMR, δ: 27.10 (C(5), 1JP,C = 11.1 Hz);
35.82 (C(6)); 36.50 (C(2), JP,C = 67.4 Hz); 38.42 (br, C(3));
39.62 (br, C(3)); 128.26 (Ph, 3JP,C = 11.1 Hz); 129.41 (Ph, 2JP,C
=
=
= 9.0 Hz); 131.25 (Ph, 4JP,C = 2.0 Hz); 133.92 (br, Ph, JP,C
1
= 91.5 Hz); 134.03 (br, Ph, 1JP,C = 89.5 Hz). 31P NMR, δ: 59.36.
MS (MALDI TOF/TOF), found: m/z 413.444 [M – H]–.
C
24H32P2O2. Calculated: M = 414.457.
3,3´ꢀHexamethyleneꢀ1,6ꢀbis(1ꢀphenylphospholane 1ꢀoxide)
(8c). Found (%): C, 70.44; H, 8.21. C26H36P2O2. Calculated
(%): C, 70.57; H, 8.20. 1H NMR, δ: 1.02—1.45 (m, 28 H, C(2)Ha,
C(2´)Ha, C(4)Ha, C(4´)Ha, C(6)H2, C(6´)H2, C(7)H2, C(7´)H2,
C(8)H2, C(8´)H2); 1.47—1.60 (m, 2 H, C(2)Ha, C(2´)Ha); 1.60—
1.68 (m, 2 H, C(4)Ha, C(4´)Ha); 1.71—1.80 (m, 2 H, C(5)Ha,
C(5´)Ha); 1.82—2.26 (m, 18 H, C(2)Hb, C(2´)Hb, C(3)H,
C(3´)H, C(4)Hb, C(4´)Hb, C(5)Hb, C(5´)Hb); 7.23—7.46, 7.52—
7.70 (both m, 20 H, Ph). 13C NMR, δ: 28.68, 28.76 (C(7)); 30.41
1
1
27.13 (C(5), JP,C = 11.1 Hz); 27.89 (C(5), JP,C = 9.1 Hz);
1
27.90 (C(5), JP,C = 9.1 Hz); 29.78, 29.84, 29.89, 29.95 (C(7));
30.84, 30.91 (C(8)); 34.24 (C(2), 1JP,C = 12.1 Hz); 34.49 (C(2),
1JP,C = 11.1 Hz); 35.28 (C(4), 2JP,C = 3.0 Hz); 35.59 (C(4), 2JP,C
=
= 4.0 Hz); 36.89, 36.92, 36.96 (C(6)); 37.14, 37.18, 37.23 (C(6));
2
2
43.15 (C(3), JP,C = 4.0 Hz); 43.17 (C(3), JP,C = 4.0 Hz);
44.31, 44. 33, 44.35 (C(3)); 128.31, 129.29 (Ph, 3JP,C = 5.0 Hz);
2
2
131.45 (Ph, JP,C = 15.1 Hz); 131.51 (Ph, JP,C = 16.1 Hz);
143.65 (br, Ph, 1JP,C = 22.1 Hz); 143.95 (br, Ph, 1JP,C = 23.1 Hz).
31P NMR, δ: –13.64, ꢀ13.23.
(C(5), 1JP,C = 67.4 Hz); 30.56, 30.75 (C(8)); 31.46 (C(5), 1JP,C
=
= 67.4 Hz); 31.82, 31.88 C(4)); 33.09, 33.13 (C(4)); 36.80 (C(2),
1JP,C = 68.4 Hz); 37.14 (br, C(6)); 37.35 (C(2), 1JP,C = 67.4 Hz);
37.43 (br, C(6)); 39.72, 39.80 (C(3)); 40.96, 41.04 (C(3)); 129.49
Synthesis of bis(phospholane 1ꢀoxides) (general procedure).
A 30% aqueous hydrogen peroxide (0.7 mL, 6 mmol) was added
slowly dropwise to a solution of bis(phospholane) (3 mmol)
synthesized according to the procedure described above in
chloroform (8 mL) with vigorous stirring, and the mixture was stirred
for 1 h. Then, the mixture was washed with water (3×5 mL), the
organic layer was dried with MgSO4. The solvent was evaporated,
the residue was subjected to chromatography on silica gel
(hexane—ethyl acetate—methanol, 5 : 3 : 1).
3
2
(Ph, JP,C = 11.1 Hz); 130.70 (Ph, JP,C = 9.0 Hz); 132.46,
135.37 (br, Ph, 1JP,C = 89.5 Hz); 135.47 (br, Ph, 1JP,C = 89.5 Hz).
31P NMR, δ: 59.24. MS (MALDI TOF/TOF), found: m/z
441.107 [M – H]–. C26H36P2O2. Calculated: M = 442.510.
Synthesis of bis(phospholane 1ꢀsulfides) (general procedure).
Sulfur (0.192 g, 6 mmol) was added to a solution of bisꢀ
phospholane (3 mmol) synthesized according to the procedure
described above in dichloromethane (10 mL) with cooling. After
stirring for 4 h, the reaction mixture was filtered through a short
layer of silica gel, the solvent was evaporated.
3,3´ꢀEthyleneꢀ1,2ꢀbis(1ꢀphenylphospholane 1ꢀsulfide) (9a).
Found (%): C, 62.93; H, 6.70. C22H28P2S2. Calculated (%):
C, 63.13; H, 6.74. 1H NMR, δ: 1.49—1.71 (m, 10 H, C(4)Ha,
C(4´)Ha, C(6)H2, C(6´)H2); 1.87—2.05 (m, 6 H, C(2)Ha,
C(2´)Ha, C(4)Ha, C(4´)Ha); 2.14—2.53 (m, 16 H, C(2)Hb,
C(2´)Hb, C(3)H, C(3´)H, C(4)Hb, C(4´)Hb, C(5)Ha, C(5´)Ha,
C(5)Hb, C(5´)Hb); 2.58—2.72 (m, 4 H, C(2)Hb, C(2´)Hb,
C(5)Hb, C(5´)Hb); 7.47—7.56, 7.85—7.93 (both m, 20 H, Ph).
13C NMR, δ: 32.14 (br, C(4)); 33.93 (br, C(4)); 34.16, 34.23,
3,3´ꢀEthyleneꢀ1,2ꢀbis(1ꢀphenylphospholane 1ꢀoxide) (8a).
Found (%): C, 68.11; H, 7.27. C22H28P2O2. Calculated (%):
1
C, 68.38; H, 7.30. H NMR, δ: 1.29—1.65 (m, 12 H, C(2)Ha,
C(2´)Ha, C(4)Ha, C(4´)Ha, C(6)H2, C(6´)H2); 1.65—1.73 (m, 2 H,
C(2)Ha, C(2´)Ha); 1.73—1.84 (m, 2 H, C(4)Ha, C(4´)Ha); 1.85—
1.95 (m, 2 H, C(5)Ha, C(5´)Ha); 1.96—2.08 (m, 4 H, C(3)H,
C(3´)H, C(5)Ha, C(5´)Ha); 2.08—2.41 (m, 14 H, C(2)Hb,
C(2´)Hb, C(3)H, C(3´)H, C(4)Hb, C(4´)Hb, C(5)Hb, C(5´)Hb);
7.43—7.52, 7.66—7.73 (both m, 20 H, Ph). 13C NMR, δ: 29.36
1
1
(C(5), JP,C = 67.4 Hz); 29.39 (C(5), JP,C = 67.4 Hz); 29.44
1
1
(C(5), JP,C = 68.4 Hz); 29.46 (C(5), JP,C = 68.4 Hz); 30.44
(C(5), 1JP,C = 66.4 Hz); 30.84, 30.91, 30.95, 31.01 (C(4)); 32.13,
32.19, 32.26, 32.30 (C(4)); 33.86, 33.99, 34.06, 34.19, 34.25,
34.31, 34.38, 34.45 (C(6)); 35.91 (C(2), 1JP,C = 67.4 Hz); 35.94
1
34.37, 34.49, 35.55 (C(6)); 35.74 (br, C(5), JP,C = 54.3 Hz);
36.61 (br, C(5), JP,C = 53.3 Hz); 39.50, 39.58, 39.66, 39.76,
39.80, 39.84, 39.89, 39.97 (C(3)); 41.36, 41.40, 41.44, 41.46,
41.64, 41.68, 41.71, 41.74 (C(3)); 41.82 (C(2), 1JP,C = 54.4 Hz);
41.98 (br, C(2), 1JP,C = 54.4 Hz); 42.47 (C(2), 1JP,C = 55.4 Hz);
42.60 (br, C(2), 1JP,C = 55.4 Hz); 128.36 (Ph, 3JP,C = 12.1 Hz);
1
1
1
(C(2), JP,C = 67.4 Hz); 35.97 (C(2), JP,C = 66.4 Hz); 36.00
1
1
(C(2), JP,C = 66.4 Hz); 36.29 (C(2), JP,C = 68.4 Hz); 36.34
1
1
(C(2), JP,C = 68.4 Hz); 36.39 (C(2), JP,C = 68.4 Hz); 36.45
(C(2), 1JP,C = 68.4 Hz); 38.72, 38.76, 38.80, 38.86, 38.96, 39,05,
30.10, 39.18 (C(3)); 39.75, 39.83, 39.91, 40.09, 40.18 (C(3));
2
129.96 (Ph, JP,C = 10.1 Hz); 131.19 (Ph, J = 3.0 Hz); 133.47
(br, Ph, JP,C = 70.4 Hz); 133.53 (br, Ph, JP,C = 70.4 Hz).
1
1
3
2
128.36 (Ph, JP,C = 11.1 Hz); 129.48 (Ph, JP,C = 9.0 Hz);
131.37 (Ph, JP,C = 5.0 Hz); 133.87 (br, Ph, JP,C = 90.5 Hz);
133.95 (br, Ph, 1JP,C = 89.5 Hz). 31P NMR, δ: 59.15.
31P NMR, δ: 57.46.
4
1
3,3´ꢀTetramethyleneꢀ1,4ꢀbis(1ꢀphenylphospholane 1ꢀsulfide)
(9b). Found (%): C, 64.41; H, 7.18. C24H32P2S2. Calculated (%):
C, 64.55; H, 7.22. 1H NMR, δ: 1.29—1.57 (m, 18 H, C(4)Ha,
C(4´)Ha, C(6)H2, C(6´)H2, C(7)H2, C(7´)H2); 1.78—1.98 (m, 6 H,
C(2)Ha, C(2´)Ha, C(4)Ha, C(4´)Ha); 2.06—2.45 (m, 16 H,
C(2)Hb, C(2´)Hb, C(3)H, C(3´)H, C(4)Hb, C(4´)Hb, C(5)Ha,
C(5´)Ha, C(5)Hb, C(5´)Hb); 2.51—2.65 (m, 4 H, C(2)Hb,
C(2´)Hb, C(5)Hb, C(5´)Hb); 7.41—7.49, 7.80—7.88 (both m,
20 H, Ph). 13C NMR, δ: 28.02 (br, C(7)); 32.14 (C(4), JP,C
= 4.0 Hz); 33.89 (C(4), JP,C = 2.0 Hz); 35.47, 35.56, 35.58,
35.67, 35.71, 35.77, 35.83 (C(6)); 35.83 (C(5), 1JP,C = 53.3 Hz);
36.71 (C(5), 1JP,C = 53.3 Hz); 39.90, 39.96, 40.02 (C(3)); 41.87
3,3´ꢀTetramethyleneꢀ1,4ꢀbis(1ꢀphenylphospholane 1ꢀoxide)
(8b). Found (%): C, 69.31; H, 7.75. C24H32P2O2. Calculated
(%): C, 69.55; H, 7.78. 1H NMR, δ: 1.20—1.48 (m, 20 H, C(2)Ha,
C(2´)Ha, C(4)Ha, C(4´)Ha, C(6)H2, C(6´)H2, C(7)H2,
C(7´)H2); 1.52—1.63 (m, 2 H, C(2)Ha, C(2´)Ha); 1.63—1.75
(m, 2 H, C(4)Ha, C(4´)Ha); 1.77—1.97 (m, 6 H, C(3)H, C(3´)H,
C(5)Ha, C(5´)Ha); 1.97—2.32 (m, 14 H, C(2)Hb, C(2´)Hb,
C(3)H, C(3´)H, C(4)Hb, C(4´)Hb, C(5)Hb, C(5´)Hb); 7.34—
7.43, 7.58—7.66 (both m, 20 H, Ph). 13C NMR, δ: 27.41, 27.45,
27.53, 27.56 (C(7)); 29.05 (br, C(5), 1JP,C = 66.4 Hz); 30.12 (br,
C(5), 1JP,C = 66.4 Hz); 30.45, 30.50, 30.53, 30.56 (C(4)); 31.80
(br, C(4)); 35.49 (br, C(2), 1JP,C = 67.4 Hz); 35.65, 35.69, 35.77,
2
=
2
1
1
(br, C(3)); 42.23 (C(2), JP,C = 53.3 Hz); 42.58 (C(2), JP,C
= 54.3 Hz); 128.30 (Ph, JP,C = 12.1 Hz); 129.93 (Ph, JP,C
=
=
3
2

Catalytic cycloalumination
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 10, October, 2015
2497
= 10.1 Hz); 131.11 (Ph, J = 3.0 Hz); 133.56 (br, Ph, 1JP,C = 70.4 Hz);
133.62 (br, Ph, 1JP,C = 70.4 Hz). 31P NMR, δ: 57.62.
8. W. Tang, X. Zhang, Angew. Chem., Int. Ed., 2002, 41, 1612.
9. (a) U. M. Dzhemilev, A. G. Ibragimov, J. Organomet. Chem.,
2010, 695, 1085; (b) U. M. Dzhemilev, V. A. D´yakonov,
Hydroꢀ, Carboꢀ and Cycloalumination of Unsaturated
Compounds, in Modern Organoaluminum Reagents:
Preparation, Structure, Reactivity and Use, Eds S. Woodward,
S. Dagorne, Berlin Heidelberg, Springer, 2013, V. 41, p. 312;
(c) V. A. D´yakonov, O. A. Trapeznikova, A. de Meijere,
U. M. Dzhemilev, Chem. Rev., 2014, 114, 5775; (d) V. A.
D´yakonov, U. M. Dzhemilev, Reactions in Organic and
Organometallic Synthesis; NOVA Sci. Publ.: New York,
2010, p. 96.
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Received January 29, 2015;
in revised form July 7, 2015