Synthesis and transformations of metallacycles 40. Catalytic cycloalumination in the synthesis of 3-substituted phospholanes

Article abstract of DOI:10.1007/s11172-012-0205-4

An efficient one-pot method was developed for the synthesis of 3-alkyland 3-benzyl-substituted phospholanes through the successive Cp₂ZrCl ₂-catalyzed cycloalumination of α-olefins in the presence of AlEt₃ giving the corre

Full text of DOI:10.1007/s11172-012-0205-4

1
556
Russian Chemical Bulletin, International Edition, Vol. 61, No. 8, pp. 1556—1559, August, 2012
Synthesis and transformations of metallacycles
4
0.* Catalytic cycloalumination in the synthesis of 3ꢀsubstituted phospholanes
V. A. D´yakonov, A. L. Makhamatkhanova, T. V. Tyumkina, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
1
41 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347) 284 2750. Eꢀmail: DyakonovVA@rambler.ru
An efficient oneꢀpot method was developed for the synthesis of 3ꢀalkylꢀ and 3ꢀbenzylꢀ
substituted phospholanes through the successive Cp ZrCl ꢀcatalyzed cycloalumination of
2
2

ꢀolefins in the presence of AlEt giving the corresponding aluminacyclopentanes followed by
3
the in situ replacement of the aluminum atom in the latter compounds by a P atom by means of
methyl(phenyl)dichlorophosphines. The oxidation of 3ꢀalkylꢀ and 3ꢀbenzylꢀ1ꢀmethyl(phenyl)ꢀ
phospholanes with hydrogen peroxide affords 3ꢀalkylꢀ and 3ꢀbenzylꢀ1ꢀmethyl(phenyl)ꢀ
phospholane 1ꢀoxides, respectively.
Key words: aluminacyclopentanes, dichlorophosphines, phospholanes, heterocycles, metal
complex catalysis, organoaluminum compounds, zirconium complexes.
Phosphorusꢀcontaining heterocycles have attracted
in situ reaction of aluminacyclopentane 1a with methyldiꢀ
chlorophosphine is accompanied by the replacement of
the Al atom by a P atom to form 3ꢀbenzylꢀ1ꢀmethylphosꢀ
pholane (2a) in 84% yield (Scheme 1).
firm interest from chemists due to their unique properties.
Great attention paid to this class of compounds is assoꢀ
ciated with their use as intermediates in multistep organic
synthesis,2 ligands for catalytic systems,
,3
4—6
and efficient
7
agents for medicine and agriculture. Hence, the developꢀ
ment of new preparative methods for the synthesis of phosꢀ
pholanes and their derivatives is of considerable interest.
A fairly large number of approaches to cyclic ogranoꢀ
phosphorus compounds (OPC) are available in the literaꢀ
ture. Reactions of trivalent phosphorus halides with dienes,
Scheme 1

,ꢀunsaturated carbonyl compounds, imines, and 1,2ꢀdiꢀ
8
,9
ketones are known. One of the promising approaches to
the synthesis of fiveꢀmembered phosphorusꢀcontaining
heterocycles is based on direct transformations of metalꢀ
1
0,11
lacarbocycles into cyclic OPC.
However, this method
requires the use of stoichiometric amounts of expensive 
complexes based on Zr, Ti, Hf, and Co and is difficult to
accomplish. In particular, these reactions should be perꢀ
formed at low temperature (from –90 to –78 C), due to
which this method has little practical application in modꢀ
ern organic and organometallic synthesis.
The purpose of the present study was to extend the
scope of catalytic cycloalumination of unsaturated comꢀ
pounds1
2,13
in the synthesis of phospholanes starting from
3
ꢀsubstituted aluminacyclopentanes, which are prepared
in situ by the reaction of ꢀolefins with Et Al in the presꢀ
3
ence of Cp ZrCl , and phosphorus alkylꢀ or aryldihalides.
2
2
Initially, we chose 3ꢀbenzylꢀ1ꢀethylaluminacycloꢀ
pentane (1a) as a model compound. We found that the
[
Zr] = Cp ZrCl2
2
R = Bn (a), Bu (b), Hex (c)
*
For Part 39, see Ref. 1.
R´ = Me (2a, 4a), Ph (3a—c, 5a—c)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1540—1543, August, 2012.
066ꢀ5285/12/6108ꢀ1556 © 2012 Springer Science+Business Media, Inc.
1

Synthesis of 3ꢀsubstituted phospholanes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 8, August, 2012
1557
The reaction of 3ꢀbenzylꢀ1ꢀethylaluminacyclopentane
1a) with phenyldichlorophosphine affords 3ꢀbenzylꢀ1ꢀ
phenylphospholane (3a) in 82% yield.
Under the conditions used, 3ꢀalkylꢀsubstituted alumiꢀ
nacyclopentanes 1b—c react with phenyldichlorophosꢀ
phine to form 3ꢀbutylꢀ1ꢀphenylphospholane (3b) and
1ꢀoxides (5a—c) was also made based on the 2D homoꢀ
and heteronuclear correlation spectra (COSYHH, HSQC,
C—H HMBC, P—H HMBC). The stereochemistry of the
isomers was determined based on the results of quantum
chemical calculations (PBE/3 and MP2) of the relative
thermodynamic parameters (Gотн) for all synthesized
(
phospholanes (Gcis > Gtrans by 0.5—1.5 kcal mol– ).
1
16
3
ꢀhexylꢀ1ꢀphenylphospholane (3c) in 92 and 91% yields,
respectively.
The synthesized phospholanes 2a and 3a—c readily
react with H O2 in chloroform to give phospholane
Actually, the upfield shifts of the signals of the carbon
atoms (for example, in compound cisꢀ2a) for P—CH and
3
CH Ph can be attributed to the intramolecular 1ꢀ4ꢀsyn
2
2
1
ꢀoxides 4a and 5a—c, respectively, in quantitative yields.
The H and C NMR spectra of the synthesized comꢀ
interaction between these groups of atoms.
1
13
Therefore, the replacement of the aluminum atom by
phosphorus in fiveꢀmembered aluminacarbocycles is an
efficient tool for the construction of cyclic organophosꢀ
phorus compounds in one preparative step. In the nearest
future, this approach will be used in the synthesis of
phosphacyclopentanes with different structures, as well as
of macrocyclic diꢀ and polyphosphorus compounds.
pounds show a double set of signals associated with the
presence of two stereoisomers, which are formed due to
the high barrier to inversion of configuration at the phosꢀ
phorus atom.1 The cis to trans isomer ratio varies dependꢀ
ing on the structure of the substituent at the phosphorus
atom. Thus, there is a large difference in the integrated
4
13
intensities of the signals in the C NMR spectrum of
methylꢀsubstituted compound 2a, the ratio being equal to
Experimental
2
3
: 1. The assignment of the signals for each isomer of
ꢀbenzylꢀ1ꢀmethylphospholane (2a) was made based on
The chromatographic analysis was performed on a Shimꢀ
adzu GCꢀ9A instrument; a 2000×2 mm column; stationary
phase SEꢀ30 silicone (5%) on Chromaton NꢀAWꢀHMDS
0.125—0.160 mm); helium as the carrier gas (30 mL min );
the results of 2D NMR spectroscopy (HSQC, COSYHH,
HMBC). It was found that all signals of the major compoꢀ
nent of the mixture are at lower field compared to the
minor component. The exceptions are the chemical shifts
of the carbon atoms in position 4, for which the reverse
order of the signals is observed. The largest difference
–1
(
temperature programming from 50 to 300 C at a rate of
–1
1
13
31
8
C min . The H, C, and P NMR spectra were recorded
13
on a Bruker Avanceꢀ400 spectrometer (100.58 MHz for C,
1
31

 = trans – cis = 2.4 ppm was found for the bridgehead
400.00 MHz for H, and 161.92 MHz for P) in CDCl3. The
positiveꢀion mass spectra were obtained in the reflection mode
on a MALDI TOF/TOF AutoflexꢀIII Bruker instrument using
31
carbon atoms C(3). The P NMR spectrum shows the
following two signals: a lowerꢀintensity signal at  35.0
and a higherꢀintensity signal at  –34.4 corresponding to
the region of tertiary phosphines.15 The presence of the
phosphorus atom in the fiveꢀmembered ring causes douꢀ
blet splitting of the signals for ꢀ, ꢀ, and ꢀcarbon atoms
2
,5ꢀdihydrobenzoic acid (2,5ꢀDHB) and ꢀcyanoꢀ4ꢀhydroxyꢀ
cinnamic acid (HCCA) as the matrix. Elemental analyses were
carried out on a Karlo Erba elemental analyzer, model 1106.
Thinꢀlayer chromatography was performed on Silufol UVꢀ254
plates using a 5 : 3 : 1 hexane—ethyl acetate—methanol system;
13
in the C NMR spectrum with the corresponding conꢀ
stants J , J , and JP,C. The largest value of the spinꢀ
the visualization was performed with I . The column chromatoꢀ
2
1
2
3
graphy was carried out using silica gel (Acros, 0.060—0.200 mm).
The yields of the products were determined by GLC using undeꢀ
cane as the internal standard. The isomer ratio was estimated
P,C
P,C
spin coupling constant was observed for the CH group at
3
the phosphorus atom (JP,C = 28.4 Hz for both isomers),
whereas the coupling constants for the C(2) and C(5)
atoms with the phosphorus atom are 14.2—17.2 and
1
13
from the intensities of the signals in the H and C NMR specꢀ
tra. The reactions with organometallic compounds were perꢀ
formed under a stream of dry argon. The solvents were dried and
distilled immediately before use; Cp ZrCl was synthesized acꢀ
1
1.1—14.2 Hz, respectively. The replacement of the meꢀ
2
2
thyl substituent by a phenyl group leads to an increase in
the spinꢀspin coupling constant to 15.8—20.5 Hz for C(2)
and 14.2—20.0 Hz for C(5) for compounds 3a—c. In
this case, the chemical shift of the phosphorus atom in
these compounds also substantially changes (to –14.1 to
17
cording to a known procedure. Commercial phosphines (Acros)
and Et Al (92%) (Redkino pilotꢀproduction plant) were used.
Synthesis of 3ꢀalkylꢀ and 3ꢀbenzylꢀ1ꢀmethyl(phenyl)phosꢀ
pholanes (general procedure). Toluene (25 mL), Cp ZrCl (0.298 g,
1 mmol), olefin (10 mmol), and AlEt3 (1.8 mL, 12 mmol) were
sequentially placed in a glass reactor with stirring under a dry
argon atmosphere at 0 C. The temperature was brought to room
temperature (~20 C), and the reaction mixture was stirred for
2 h. Then the reaction mixture was cooled to –10 or –15 C,
after which methylꢀ or phenyldichlorophosphine (12 mmol) was
added dropwise. The reaction mixture was stirred at room temꢀ
3
2
2
–
12.6 ppm). In oxidized phosphacyclopentanes 4a and
5
a—c, the endocyclic ꢀcarbon atoms C(2) and C(5) have
1
31
JP,C  88—101 Hz. In the P NMR spectra of comꢀ
pounds 4a and 5a—c, the signals are shifted in the positive
direction to ~59—67 ppm, which is consistent with the
1
1
5
1
13
literature data. The assignment of signals in the H, C,
perature for 30 min and workedꢀup with a saturated NH Cl
aqueous solution. The reaction products were extracted with
4
31
and P NMR spectra of 3ꢀbenzylꢀ1ꢀmethylphospholane
ꢀoxide (4a), 3ꢀalkylꢀ and 3ꢀbenzylꢀ1ꢀphenylphospholane
1
diethyl ether and dried over MgSO . The solvent was evaporatꢀ
4

1558
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 8, August, 2012
D´yakonov et al.
ed, and the target phospholanes were isolated by distillation
in vacuo. All operations were carried out under a stream of argon.
Synthesis of 3ꢀalkylꢀ and 3ꢀbenzylꢀ1ꢀmethyl(phenyl)phosꢀ
pholane 1ꢀoxides (general procedure). A 30% hydrogen peroxide
solution (0.7 mL, 6 mmol) was slowly added dropwise with vigꢀ
orous stirring to a solution of 3ꢀalkylꢀ or 3ꢀbenzylꢀ1ꢀalkylꢀ
C(4)H ); 2.19—2.33 (m, 1 H, C(5)H ); 2.39 (dd, 1 H, C(2)H ,
b
b
b
2
3
J = 13.3 Hz, J = 7.2 Hz); 7.28, 7.34, 7.40—7.48 (m, 5H, Ph);
3
cis isomer: 0.91 (t, 3 H, C(4´)H , J = 7.2 Hz); 1.26—1.39 (m, 5 H,
3
C(2´,3´)H , C(4)H ); 1.39—1.58 (m, 3 H, C(1´)H , C(2)H );
2
a
2
a
1.84—1.99 (m, 2 H, C(3)H, C(5)H ); 2.02—2.19 (m, 2 H,
a
2
3
C(4)H , C(5)H ); 2.45 (dd, 1 H, C(2)H , J = 12.9 Hz, J = 7.5 Hz);
b
b
b
1
3
(
phenyl)phospholane (5 mmol), which were synthesized accordꢀ
7.28, 7.34, 7.40—7.48 (m, 5 H, Ph). C NMR, , trans isomer:
14.10 (C(4´)); 22.94 (C(3´)); 26.00 (C(5), JP,C = 17.4 Hz); 30.98
(C(2´)); 33.32 (C(2), JP,C = 15.8 Hz); 34.18 (C(4)); 35.53 (C(1´),
ing to the aboveꢀdescribed procedure, in chloroform (10 mL).
The reaction mixture was stirred for 1 h and washed with water
(
3×5 mL), the organic layer was dried over MgSO , the solvent
JP,C = 4.7 Hz); 43.22 (C(3)); 127.33, 128.28, 130.42 (JP,C =
4
was evaporated, and the residue was chromatographed on silica
gel (hexane : ethyl acetate : methanol = 5 : 3 : 1).
= 23.7 Hz), 142.30 (JP,C = 36.3 Hz) (Ph); cis isomer: 14.10
(C(4´)); 22.87 (C(3´)); 26.75 (C(5), JP,C = 12.6 Hz); 31.06
(C(2´)); 33.07 (C(2), JP,C = 15.8 Hz); 33.48 (C(4), JP,C = 6.3 Hz);
35.80 (C(1´), JP,C =6.3 Hz); 42.09 (C(3), JP,C = 6.3 Hz); 127.37,
3
ꢀBenzylꢀ1ꢀmethylphospholane (2a) (trans : cis = 2 : 1). Yield
8
4%. B.p. 121—125 C (6 Torr). Found (%): C, 75.6; H, 8.8.
1
C H P. Calculated (%): C, 74.97; H, 8.91. H NMR, , trans
128.23, 130.50 (J
P NMR, , transꢀ and cis isomers: –12.55. MS (MALDI TOF/
TOF), found: m/z 221.331 [M + H] . C H PH. Calculated:
= 23.7 Hz), 142.51 (JP,C = 36.3 Hz) (Ph).
12
17
P,C
31
isomer: 1.06 (m, 4 H, PC(6)H , C(2)H ); 1.48—1.68 (m, 3 H,
3
a
+
C(4)H C(5)H ); 1.98—2.20 (m, 3 H, C(3)H, C(2)H , C(4)H );
a,
2
b
b
12 17
3
2
.80 (t, 2 H, C(1´)H , J = 5.8 Hz); 7.20—7.25, 7.30—7.35 (m, 5 H,
M = 220.138.
2
Ph); cis isomer: 1.00—1.03 (m, 3 H, PC(6)H ); 1.32—1.42 (m, 3 H,
3ꢀHexylꢀ1ꢀphenylphospholane (3c) (trans : cis = 3 : 2). Yield
91%. B.p. 191—194 C (9 Torr). Found (%): C, 77.3; H, 10.2.
3
C(2)H , C(4)H , C(5)H ); 2.0—2.15 (m, 3 H, C(2)H , C(4)H ,
a
a
a
b
b
2
1
C H P. Calculated (%): C, 77.38; H, 10.15. H NMR, , trans
16 25
C(5)H ); 2.38 (m, 1 H, C(3)H); 2.68 (dd, 1 H, C(1´)H , J = 12 Hz,
b
a
3
3
2
3
J = 7.3 Hz); 2.72 (dd, 1 H, C(1´)H , J = 12 Hz, J = 7.3 Hz);
.20—7.25, 7.30—7.35 (m, 5 H, Ph). C NMR, , trans isomer:
4.24 (C(6), JP,C = 28.4 Hz); 26.80 (C(5), JP,C = 11.1); 33.08
isomer: 0.93 (t, 3 H, C(6´)H , J = 7.2 Hz); 1.26—1.40 (m, 10 H,
b
3
1
3
7
1
C(1´)H , C(2´)H , C(3´)H , C(4´)H , C(5´)H ); 1.41—1.62
2
2
2
2
2
(m, 2 H, C(2)H , C(4)H ); 1.84—2.01 (m, 2 H, C(3)H, C(5)H );
a
a
a
(
C(4), JP,C = 6.3 Hz); 34.20 (C(2), JP,C = 17.4 Hz); 42.75 (C(1´),
2.13—2.20 (m, 1 H, C(4)H ); 2.20—2.32 (m, 1 H, C(5)H ); 2.39
b b
2
3
JP,C = 7.9 Hz); 45.56 (C(3), JP,C = 3.2 Hz); 125.87, 128.28,
1
2
(dd, 1 H, C(2)H , J = 13.3 Hz, J = 7.2 Hz); 7.28, 7.35, 7.40—7.48
b
3
28.80, 141.66 (Ph); cis isomer: 13.94 (C(6), JP,C = 28.4 Hz);
6.69 (C(5), JP,C = 14.2 Hz); 33.60 (C(2), JP,C = 14.2 Hz); 34.18
(m, 5 H, Ph); cis isomer: 0.93 (t, 3 H, C(6´)H , J = 7.2 Hz);
3
1.27—1.50 (m, 10 H, C(1´)H , C(2´)H , C(3´)H , C4´)H ,
2
2
2
2
(
C(4), JP,C = 3.2 Hz); 41.94 (C(1´), JP,C = 4.7 Hz); 43.16 (C(3),
JP,C = 7.9 Hz); 125.87, 128.28, 128.87, 141.66 (Ph). 31P NMR,
, trans isomer: –34.41; cis isomer: –35.07. MS (MALDI
C(5´)H ); 1.50—1.61 (m, 2 H, C(2)H , C(4)H ); 1.83—2.01
2
a
a
(m, 2 H, C(3)H, C(5)H ); 2.02—2.22 (m, 2 H, C(4)H , C(5)H );
a
b
b
2
3

2.45 (dd, 1 H, C(2)H , J = 12.9 Hz, J = 7.5 Hz); 7.28, 7.35,
7.40—7.48 (m, 5 H, Ph). C NMR, , trans isomer: 14.10
b
+
13
TOF/TOF), found: m/z 192.998 [M + H] . C H PH. Calcuꢀ
12
17
lated: M = 192.107.
ꢀBenzylꢀ1ꢀphenylphospholane (3a) (trans : cis = 3 : 2). Yield
2%. B.p. 198—202 C (6 Torr). Found (%): C, 80.2; H, 7.6.
(C(6´)); 22.66 (C(5´)); 26.06 (C(5), JP,C = 17.4 Hz); 28.72
(C(2´)); 29.56 (C(3´)); 31.85 (C(4´)); 33.43 (C(2); JP,C = 17.4 Hz);
34.21 (C(4), JP,C = 3.2 Hz); 35.87 (C(1´), JP,C = 6.3 Hz); 43.28
3
8
1
C H P. Calculated (%):C, 80.29; H, 7.53. H NMR, , trans
(C(3)); 127.17, 128.21, 130.36 (JP,C = 23.7 Hz), 142.73 (JP,C =
17
19
isomer: 1.42—1.50 (m, 1 H, C(4)H ); 1.63—1.73 (m, 1 H,
= 36.3 Hz) (Ph); cis isomer: 14.10 (C(6´)); 22.66 (C(5´)); 26.86
(C(5), JP,C = 14.2 Hz); 28.83 (C(2´)); 29.50 (C(3´)); 31.85
(C(4´)); 33.19 (C(2), JP,C = 20.5 Hz); 34.52 (C(4), JP,C = 6.3 Hz);
36.13 (C(1´), JP,C = 7.9 Hz); 42.10 (C(3), JP,C = 6.3 Hz); 127.17,
a
C(2)H ); 1.83—1.91 (m, 1 H, C(5)H ); 2.02—2.12 (m, 2 H,
a
a
C(4)H , C(5)H ); 2.24 (m, 1 H, C(3)H); 2.30—2.40 (m, 1 H,
b
b
C(2)H ); 2.75 (d, 1 H, C(1´)H ); 2.77 (d, 1 H, C(1´)H ,J = 4.3 Hz);
b
a
b
7
.15—7.47 (m, 10 H, Ar); cis isomer: 1.42—1.50 (m, 1 H,
128.17, 130.42 (J
P NMR, , trans isomer: –13.74; cis isomer: –14.12. MS
(MALDI TOF/TOF), found: m/z 249.166 [M + H] . C H PH.
= 25.3 Hz), 143.09 (JP,C = 34.8 Hz) (Ph).
P,C
31
C(4)H ); 1.61 (m, 1 H, C(2)H ); 1.93—1.99 (m, 1 H, C(5)H );
2
a
a
a
+
.02—2.12 (m, 2 H, C(2)H , C(4)H ); 2.20—2.30 (m, 2 H,
b
b
12 17
C(5)H ); 2.32 (m, 1 H, C(3)H); 2.72 (d, 2 H, C(1´)H ); 7.15—7.47
Calculated: M = 248.169.
b
2
13
(
m, 10 H, Ar). C NMR, , trans isomer: 25.88 (C(5), JP,C
=
3ꢀBenzylꢀ1ꢀmethylphospholane 1ꢀoxide (4a) (trans : cis =
= 2 : 1). R = 0.71. Found (%): C, 60.4; H, 8.3. C H OP.
=
20 Hz); 33.15 (C(2), JP,C = 20 Hz); 33.95 (C(4), JP,C = 7.9 Hz);
f
12 17
1
4
1
1.99 (C(1´), JP,C = 4.7 Hz); 43.79 (C(3), JP,C = 7.9 Hz); 125.90,
Calculated (%): C, 60.21; H, 8.23. H NMR, , trans isomer:
1.20—1.23 (m, 1 H, C(5)H ); 1.23—1.31 (m, 1 H, C(2)H ); 1.62
28.30, 128.85, 141.34 (CH Ph); 127.31, 128.30, 130.39
2
a
a
(
2
(
1
JP,C = 25.3 Hz); 142.42 (JP,C = 34.8 Hz) (PPh); cis isomer:
6.54 (C(5), JP,C = 15.8 Hz); 32.99 (C(2), JP,C = 20.5 Hz); 34.27
C(4), JP,C = 4.7 Hz); 42.15 (C(1´), JP,C = 7.9 Hz); 45.01 (C(3));
25.92, 128.30, 128.82, 141.45 (CH Ph); 127.31, 128.30, 130.45
(s, 3 H, PC(6)H ); 1.68—1.72 (m, 1 H, C(4)H ); 1.99—2.10
3 a
(m, 3 H, C(2)H , C(4)H , C(5)H ); 2.51 (1 H, C(3)H, J = 6);
b b b
3
2.69 (d, 2 H, C(1´)H , J = 8.0 Hz); 7.13—7.17, 7.21—7.26 (m, 5 H,
2
Ph); cis isomer: 1.20—1.30 (m, 2 H, C(2)H , C(5)H ); 1.66
2
a
a
31
(
JP,C = 23.7 Hz), 142.97 (JP,C = 36.3 Hz) (PPh). P NMR, ,
(s, 3 H, PC(6)H ); 1.67—1.72 (m, 1 H, C(4)H ); 1.79—1.86
3 a
transꢀ and cis isomers: –13,58. MS (MALDI TOF/TOF), found:
(m, 1 H, C(5)H ); 2.00—2.16 (m, 3 H, C(3)H, C(2)H , C(4)H );
b b b
+
m/z 255.432 [M + H] . C H PH. Calculated: M = 254.122.
2.72 (d, 2 H, C(1´)H , J = 8.2 Hz); 7.21—7.26 (m, 5 H, Ph).
17
19
2
13
3
ꢀButylꢀ1ꢀphenylphospholane (3b) (trans : cis = 3 : 2). Yield
C NMR,  trans isomer: 18.01 (C(6)); 30.24 (C(5); JP,C =
9
2%. B.p. 172—177 C (10 Torr). Found (%): C, 76.3; H, 9.8.
= 107.4); 30.52 (C(4)); 34.21 (C(2), J = 107.4 Hz); 40.90 (C(3),
J = 12.6 Hz); 42.24 (C(1´), JP,C = 22.1 Hz); 126.46, 128.59,
128.89, 139.59 (Ph); cis isomer: 17.39 (C(6)); 29.58 (C(5),
JP,C = 107.4 Hz); 31.34 (C(4)); 35.14 (C(2); JP,C = 107.4 Hz);
40.67 (C(3), JP,C = 12.6 Hz); 42.17 (C(1´), JP,C = 22.1 Hz);
1
C H P. Calculated (%): C, 76.33; H, 9.61. H NMR, , trans
isomer: 0.91 (t, 3 H, C(4´)H , J = 7.2 Hz); 1.26—1.41 (m, 5 H,
C(2´,3´)H , C(4)H ); 1.37—1.60 (m, 3 H, C(1´)H C(2)H );
1
14
21
3
3
2
a
2,
a
.85—2.00 (m, 2 H, C(3)H, C(5)H ); 2.05—2.19 (m, 1 H,
a

Synthesis of 3ꢀsubstituted phospholanes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 8, August, 2012
1559
1
6
2
26.46, 128.59, 128.99, 139.84 (Ph). 31P NMR, , trans isomer:
7.22; cis isomer: 67.73. MS (MALDI TOF/TOF), found: m/z
2.06—2.15 (m, 1 H, C(5)H ); 2.15—2.38 (m, 3 H, C(3)H,
b
13
C(2)H , C(4)H ); 7.36—7.50, 7.60—7.75 (m, 5 H, Ph). C NMR,
b
b
+
09.165 [M + H] . C H PH. Calculated: M = 208.102.
, trans isomer: 13.88 (C(6´)); 22.31 (C(5´)); 27.59 (C(2´)); 29.05
(C(3´)); 29.86 (C(5); JP,C = 60 Hz); 31.00 (C(4), JP,C
12
17
3
ꢀBenzylꢀ1ꢀphenylphospholane 1ꢀoxide (5a) (trans : cis =
=
=
3 : 2). R = 0.42. Found (%): C, 75.7; H, 7.2. C H OP.
= 11.1 Hz); 31.47 (C(4´)); 35.65 (C(2), JP,C = 88.5 Hz); 36.02
(C(1´), JP,C = 6.3 Hz); 39.91 (C(3), JP,C = 14.2 Hz); 128.31,
129.54, 131.30, 134.23 (PPh); cis isomer: 13.80 (C(6´)); 22.31
(C(5´)); 27.48 (C(2´)); 28.99 (C(3´)); 29.20 (C(5), JP,C = 66.4 Hz);
f
17 19
1
Calculated (%): C, 75.54; H, 7.08. H NMR, , trans isomer:
1
.54—1.63 (m, 1 H, C(2)H ); 1.89—1.96 (m, 1 H, C(5)H );
a
a
2.07—2.27 (m, 4 H C(2)H , C(4)H , C(5)H ); 2.30—2.36 (m, 1 H,
b
2
b
C(3)H); 2.75 (d, 2 H, C(1´)H , J = 6,4 Hz); 7.15—7.25, 7.30
30.73 (C(4), JP,C = 7.9 Hz); 31.47 (C(4´)); 36.14 (C(1´), JP,C
=
=
2
(
m, 5 H, CH Ph); 7.45—7.55, 7.71 (m, 5 H, PPh); cis isomer:
= 6.3 Hz); 36.32 (C(2), JP,C = 88.5 Hz); 38.64 (C(3), J
2
P,C
31
1
1
.42—1.51 (m, 1 H, C(4)H ); 1.79—1.88 (m, 1 H, C(2)H );
= 12.6 Hz); 128.43, 129.64, 131.33, 134.16 (PPh). P NMR, ,
trans isomer: 59.40; cis isomer: 59.50. MS (MALDI TOF/TOF),
a
a
.89—1.96 (m, 1 H, C(5)H ); 2.07—2.27 (m, 2 H, C(2)H ,
a
b
+
C(5)H ); 2.30—2.36 (m, 1 H, C(4)H ); 2.73 (m, 1 H, C(3)H);
found: m/z 265.473 [M + H] . C16H25OPH. Calculated:
b
b
2
.78 (d, 2 H, C(1´)H , J = 6 Hz); 7.15—7.25, 7.30 (m, 5 H,
M = 264.164.
2
13
CH Ph); 7.45—7.55, 7.71 (m, 5 H, PPh). C NMR, , trans
2
isomer: 30.42 (C(5), JP,C = 104.3 Hz); 30.75 (C(4), JP,C = 7.9 Hz);
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 10ꢀ03ꢀ00046,
11ꢀ03ꢀ00103, and 11ꢀ03ꢀ97001).
3
5.57 (C(2), JP,C = 94.8 Hz); 41.89 (C(3), JP,C = 12.6 Hz); 42.34
(
C(1´), JP,C = 20 Hz); 126.16, 128.32, 128.66, 139.58 (CH Ph);
2
1
28.54, 128.66, 129.69, 131.51 (PPh); cis isomer: 29.42 (C(5),
JP,C = 104.3 Hz); 31.82 (C(4), JP,C = 7.9 Hz); 36.20 (C(2),
JP,C = 91.6 Hz); 40.58 (C(3), JP,C = 12.6 Hz); 42.22 (C(1´),
References
J
1
= 20 Hz); 126.18, 128.28, 128.66, 139.26 (CH Ph); 128.43,
P,C
2
28.66, 129.69, 131.53 (PPh). 31P NMR, , trans isomer: 59.48;
1. V. A. D´yakonov, A. A. Makarov, E. Kh. Makarova, T. V.
Tyumkina, U. M. Dzhemilev, Russ. Chem. Bull. (Int. Ed.),
2012, 61, No. 1 [Izv. Akad. Nauk, Ser. Khim., 2012, 156].
2. G. Keglevich, H. Forintos, G. M. Keseru, L. Hegedüs,
L. T ke, Tetrahedron, 2000, 56, 4823.
3. M. Yamashita, V. K. Reddy, L. N. Rao, B. Haritha, M. Maꢀ
eda, K. Suzuki, H. Totsuka, M. Takahashi, T. Oshikawa,
Tetrahedron Lett., 2003, 44, 2339.
4. L. Kollar, G. Keglevich, Chem. Rev., 2010, 110, 4257.
5. B. Breit, E. Fuchs, Chem. Commun., 2004, 694.
6. J. Klosin, C. R. Landis, Acc. Chem. Ress., 2007, 40, 1251.
7. M. Yamada, M. Yamashita, T. Suyama, J. Yamashita,
K. Asai, T. Niimi, N. Ozaki, M. Fujie, K. Maddali, S. Nakaꢀ
mura, K. Ohnishi, Bioorg. Med. Chem. Lett., 2010, 20, 5943.
8. L. D. Quin, The Heterocyclic Chemistry of Phosphorus: Sysꢀ
tems Based on the PhosphorusꢀCarbon Bond, WileyꢀInterꢀ
science, New York, 1981, p. 500.
cis isomer: 58.87. MS (MALDI TOF/TOF), found: m/z 271.331
+
[
M + H] . C H OPH. Calculated: M = 270.117.
17 19
3
ꢀButylꢀ1ꢀphenylphospholane 1ꢀoxide (5b) (trans : cis = 3 : 2).
R = 0.35. Found (%): C, 71.2; H, 8.0. C H OP. Calculatꢀ
f
14 21
1
ed (%): C, 71.16; H, 8.96. H NMR, , trans isomer: 0.91 (t, 3 H,
C(4´)H , J = 7.2 Hz); 1.29—1.39 (m, 4 H, C(2´)H , C(3´)H );
3
3
2
2
1
1
.47—1.58 (m, 3 H, C(1´)H , C(2)H ); 1.70 (m, 1 H, C(5)H );
2 a a
.75—1.83 (m, 1 H, C(4)H ); 2.00 (m, 1 H, C(3)H); 2.14—2.26
a
(
(
m, 3 H, C(2)H , C(4)H , C(5)H ); 7.45—7.56, 7.68—7.77
b b b
3
m, 5 H, Ph); cis isomer: 0.91 (t, 3 H, C(4´)H , J = 7.2 Hz);
3
1
.29—1.39 (m, 5 H, C(2´)H , C(3´)H , C(4)H ); 1.40—1.58
2 2 a
(
m, 2 H, C(1´)H ); 1.67—1.73 (m, 1 H, C(2)H ); 2.09 (m, 1 H,
2
a
C(5)H ); 2.19 (m, 1 H, C(5)H ); 2.22—2.41 (m, 3 H, C(3)H,
a
b
13
C(2)H , C(4)H ); 7.45—7.56, 7.68—7.77 (m, 5 H, Ph). C NMR,
b
b

, trans isomer: 14.07 (C(4´)); 22.49 (C(3´)); 29.32 (C(5), JP,C
=
=
104.3 Hz); 29.88 (C(2´)); 30.76 (C(4), JP,C = 9.5 Hz); 35.62
(
(
C(2), JP,C = 88.5 Hz); 35.74 (C(1´), JP,C = 9.5 Hz); 39.95
C(3), JP,C = 12.6 Hz); 128.61, 129.89, 131.66, 134.07 (PPh);
9. G. Markl, Angew. Chem. Int. Ed., 1965, 12, 1023.
10. Y. Zhou, X. Yan, C. Xi, Tetrahedron Lett., 2010, 51, 6136.
11. P. J. Fagan, W. A. Nugent, J. C. Calabrese, J. Am. Chem.
Soc., 1994, 116, 1880.
12. U. M. Dzhemilev, Mendeleev Commun., 2008, 18, 1.
13. U. M. Dzhemilev, A. G. Ibragimov, Usp. Khim., 2000, 69,
134 [Russ. Chem. Rev. (Engl. Transl.), 2000, 69)].
14. V. M. Potapov, Stereokhimiya [Stereochemistry], Khimiya,
Moscow, 1988, 464 pp. (in Russian).
cis isomer: 14.07 (C(4´)); 22.49 (C(3´)); 29.74 (C(2´)); 30.34
(
(
(
3
C(5), JP,C = 104.3 Hz); 32.02 (C(4), JP,C = 9.5 Hz); 35.87
C(1´), JP,C = 11.1 Hz); 36.30 (C(2), JP,C = 86.9 Hz); 38.68
C(3), J
= 12.6 Hz); 128.72, 129.79, 131.66, 134.99 (PPh).
P,C
1
P NMR, , trans isomer: 60.11; cis isomer: 60.20. MS
MALDI TOF/TOF), found: m/z 237.413 [M + H] . C H PH.
+
(
12
17
Calculated: M = 236.133.
3
ꢀHexylꢀ1ꢀphenylphospholane 1ꢀoxide (5c) (trans : cis = 3 : 2).
15. O. Kühl, Phosphorusꢀ31 NMR Spectroscopy: a Concise Introꢀ
duction for the Synthetic Organic and Organometallic Chemist,
Springer, Berlin, 2008, p. 131.
16. D. N. Laikov, Chem. Phys. Lett., 1997, 281, 151.
17. R. Kh. Freidlina, E. M. Brainina, A. N. Nesmeyanov, Dokl.
Akad. Nauk SSSR, 1969, 138, 1369 [Dokl. Chem.
(Engl. Transl.), 1969].
R = 0.44. Found (%): C, 72.7; H, 9.6. C H OP. Calculatꢀ
ed (%): C, 72.70; H, 9.53. H NMR, , trans isomer: 0.83 (t, 3 H,
C(6´)H , J = 7.2 Hz); 1.66—1.33 (m, 10 H, C(1´)H , C(2´)H ,
C(3´)H , C(4´)H , C(5´)H ); 1.58—1.70 (m, 1 H, C(2)H );
.70—1.80 (m, 1 H, C(4)H ); 1.80—1.90 (m, 1 H, C(5)H );
.90—2.01 (m, 1 H, C(3)H); 2.10—2.30 (m, 3 H, C(2)Hb,
f
16 25
1
3
3
2
2
2
2
2
a
1
1
a
a
C(4)H , C(5)H ); 7.36—7.50, 7.60—7.75 (m, 5 H, Ph); cis isoꢀ
b
b
3
mer: 0.83 (t, 3 H, C(6´)H , J = 7.2 Hz); 1.16—1.33 (m, 11 H,
3
C(1´)H , C(2´)H , C(3´)H , C(4´)H , C(5´)H , C(4)H );
Received April 17, 2012;
2
2
2
2
2
a
1
.37—1.53 (m, 1 H, C(2)H ); 1.82—1.91 (m, 1 H, C(5)H );
in revised form June 9, 2012
a
a