Diastereoselective synthesis of functionally substituted alkene dimers and oligomers, catalysed by chiral zirconocenes

Article abstract of DOI:10.1016/j.catcom.2018.10.032

The research addresses the reaction of terminal alkenes and propene with AlR₃ (R = Me, Et) in the presence of chiral Zr complexes, rac-[Y(η⁵-C₉H₁₀)₂]ZrCl₂ (Y = C₂H₄, SiMe₂) or (NMI)₂ZrCl₂ (NMI- η⁵–neomenthylindenyl), and methylaluminoxane. The effect of reaction conditions, catalyst and trialkylalane structure on the substrate conversion and the reaction chemo- and stereoselectivity has been studied. The reaction predominantly goes via the stage of alkene methyl(ethyl)zirconation with subsequent introduction of substrate molecules into the Zr-C bond. As a result, a diastereoselective one-pot method for the synthesis of functionally substituted linear terminal alkene dimers and propene oligomers was developed.

Full text of DOI:10.1016/j.catcom.2018.10.032

Accepted Manuscript
Diastereoselective synthesis of functionally substituted alkene
dimers and oligomers, catalysed by chiral zirconocenes
Pavel V. Kovyazin, Il'giz N. Abdullin, Lyudmila V. Parfenova
PII:
S1566-7367(18)30301-7
DOI:
Reference:
https://doi.org/10.1016/j.catcom.2018.10.032
CATCOM 5543
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
6 September 2018
19 October 2018
30 October 2018
Please cite this article as: Pavel V. Kovyazin, Il'giz N. Abdullin, Lyudmila V. Parfenova
, Diastereoselective synthesis of functionally substituted alkene dimers and oligomers,
catalysed by chiral zirconocenes. Catcom (2018), https://doi.org/10.1016/
j.catcom.2018.10.032
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ACCEPTED MANUSCRIPT
Diastereoselective Synthesis of Functionally Substituted Alkene Dimers and
Oligomers, Catalysed by Chiral Zirconocenes
Pavel V. Kovyazin, Il’giz N. Abdullin, Lyudmila V. Parfenova,*
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 450075 Ufa, Prosp.
Oktyabrya, 141, Russian Federation

ACCEPTED MANUSCRIPT
Abstract
The research addresses the reaction of terminal alkenes and propene with AlR3 (R = Me, Et) in
the presence of chiral Zr complexes, rac-[Y(η5-C9H10)2]ZrCl2 (Y = C2H4, SiMe2) or (NMI)2ZrCl2
(NMI- η5–neomenthylindenyl), and methylaluminoxane. The effect of reaction conditions,
catalyst and trialkylalane structure on the substrate conversion and the reaction chemo- and
stereoselectivity has been studied. The reaction predominantly goes via the stage of alkene
methyl(ethyl)zirconation with subsequent introduction of substrate molecules into the Zr-C bond.
As a result, a diastereoselective one-pot method for the synthesis of functionally substituted linear
terminal alkene dimers and propene oligomers was developed.
Keywords: dimers, oligomers, zirconocenes, carbometalation

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1. Introduction
Catalytic systems based on titanium-group metallocenes and methylaluminoxane (MAO)
are widely used for alkene polymerization [1], di- and oligomerization [2]-[4]. By varying the
electronic and spatial structures of the ligand in the transition metal complexes, one can control
the activity and stereoselectivity of these catalytic systems [5], [6]. There are few publications on
the use of chiral metallocene complexes in the stereoselective synthesis of alkene oligomers. For
example, the synthesis of saturated stereoregular optically active oligomers of propene catalyzed
by ansa-zirconocene-based system, (R)-[C2H4(η5-C9H10)2]ZrMe2/MAO/H2 (the molar ratio [Zr] :
[MAO] = 1:3), has been reported [7], [8]. Enantiomerically enriched propene and butene
oligomers containing a methylene double bond were obtained with the use of catalytic system
(S)-[C2H4(η5-C9H10)2]Zr(O-acetyl-(R)-mandelate)2/MAO (the molar ratio [Zr] : [MAO] = 1:100)
[9]. The reactions give saturated or unsaturated hydrocarbons, where it may be difficult to
introduce additional functional groups needed for their further application as synthons. The
enantiomerically and diastereomerically pure methyl-substituted primary alcohols were obtained
in the reaction of propene with ZnEt2 and MAO catalyzed by enantiomerically pure zirconocenes
(the molar ratio [Zr]:[MAO]:[ZnEt2] = 1:1000:(1800-5000)) followed by subsequent oxidation
[11], [12]. Functionally substituted products of 1-hexene oligomerization containing up to six
units were synthesized using ansa-5-complexes as catalysts [13], [14]. Thus, the stereoselective
oligomerization of alkenes appears to be a promising method, because it could provide one-pot
route to stereomerically pure moieties of practically useful compounds for medicinal chemistry
and industry [3], [4], [15]-[18] (Scheme 1). Meanwhile, the existing syntheses of these structural
units are multistage and occur via gradual attachment of monomer units (see, for example, Ref.
[19]-[26]).

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Scheme 1.
n
X= H, Alk
Y=
one-pot synthesis
L2ZrCl2
OH, SiR3, SiMe2Cl,
SMe2, SO3H, SCOCH3,
PO2H2, PR2O
MAO
AlR3
n
additional reactions for
double bond functionalization
structural blocks of biologically active molecules,
lubricants, synthetic motor oils, detergents,
plastificators, adhesives, selective extragents
n
Vittatalactone
(-)-Lardorule
Ionomycin (A) (C1-C10 fragment)
4,6,8,10,16,18-hexamethyldocosane
10-Norvittatalactone
Sulfoglycolipid
SL
Phthioceranic acid
Hydroxyphthioceranic acid
Thus, in order to develop the method for the one-pot synthesis of functionalized linear
terminal alkene and propene oligomers we studied the effect of the catalyst and trialkylalane
structures, as well as the reaction conditions on the catalytic system activity, chemo- and
stereoselectivity. As the stereoselective catalysts for the preparation of alkene oligomers, we
used both conformationally rigid ansa-complexes, rac-[Y(η5-C9H10)2]ZrCl2 (Y= C2H4 (1), SiMe2
(2)), and conformationally mobile bis(η5–1–neomenthylindenyl)zirconium dichloride (3)
(Scheme 2).
2. Experimental
General procedures. All operations for organometallic compounds were performed under
argon according to Schlenk technique. The zirconocenes 1-3 were prepared using the standard
procedures from ZrCl4 (99.5%, Aldrich) (rac-1 [27], rac-2 [28], 3 [29]). The solvents (hexane,
toluene) were distilled from i-Bu2AlH immediately prior to use; THF and diethyl ether were

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dried and distilled from sodium/benzophenone before use. Dichloromethane was dried over
P2O5. Commercially available 98% AlEt3, 97% AlMe3 (Aldrich) and MMAO-12 (7 wt% Al in
toluene, Sigma-Aldrich) were involved into the reactions. Terminal alkenes 1-hexene (97%,
Acros), 1-octene (99%, Acros), 1-decene (97%, Acros) and propylene (≥99%, Sigma-Aldrich)
were used.
1
The Н and 13С NMR spectra were recorded on a Bruker AVANCE-400 spectrometer (400.13
MHz (1H), 100.62 MHz (13C)). As the solvent and the internal standard, CDCl3 was employed.
1D and 2D NMR spectra (COSY HH, HSQC, HMBС) were recorded using standard Bruker
pulse sequences. Chromatographic analysis was carried out on a CARLO ERBA 1150
instrument in a helium flow, a 50000 × 0.32 mm column, ULTRA-1 stationary phase, and a
flame ionization detector. The deuterated products were analyzed by GC/MS on an automated
QP 2010 Ultra GC/MS assembled with a TD-20 Shimadzu thermal desorber.
Reaction of 1-alkenes with AlR3 (R= Me, Et) in the presence of complexes 1-3 and
MAO.
A 50 mL glass reactor mounted on a magnetic stirrer and filled with argon was charged
with catalyst (1-3) (0.0075 mmol), CH2Cl2 or C6H5CH3 (10 ml), alkene 4a-c (1.5 mmol), AlR3
(1.5 mmol) and MМАО-12 (0.3 mmol). In the case of propene (4d), the reaction media was
bubbled with alkene at 0°C, brought to room temperature and stirred for 24 hours under a
propene atmosphere (1 bar). The reaction was carried out at 20°С with continuous stirring for 72
hours. After completion of the reaction, a part of the reaction mixture was quenched with 10%
DCl at 0оС. The products were extracted with benzene and filtered, and the organic layer was
dried with Na2SO4. The product yield (5-8) was determined by analyzing the hydrolysis and
deuterolysis products by GLC and GC/MS.
The remaining reaction mixture was cooled to 0°С and oxidized by bubbling О2 for 2 h,
then kept in an oxygen atmosphere for 24 hours more. The products were quenched with HCl
and extracted by diethyl ether, and the organic layer was dried with Na2SO4, filtered, and
concentrated. Functionally substituted di- and oligomers (9, 10) were isolated by column
chromatography on silica gel using a 7 : 1 hexane : diethyl ether system. Alcohols 9 (n=1) were
isolated by column chromatography on silica gel in a 4 : 1 hexane : diethyl ether system. The
organic fractions were dried over Na2SO4.
Synthesis of silylated derivatives of propene oligomer alcohols. A 20 mL glass reactor
mounted on a magnetic stirrer and filled with argon was charged with 5 ml of toluene and 20 mg
of hydroxy- substituted propene oligomers 9-IId or 10d (0.06-0.095 mmol). At 0°C, 0.1 ml (0.25
mmol) of BuLi (2.5 M in hexane) was added dropwise to the solution. The resulting solution was
brought to room temperature and stirred for 30 minutes. Then the reactor was cooled to 0°C and

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0.04 ml (0.3 mmol) of Me3SiCl was added dropwise. The resulting mixture was brought to room
temperature and stirred for 3 hours. After that, the reaction mixture was decomposed with water;
the organic layer was collected and dried over Na2SO4. Compounds 13, 14 were obtained and
analyzed by GLC and GC-MS.
3. Results and Discussion
The reaction of alkenes with AlR3 in the presence of 0.5 mol% of complexes 1-3 and MAO
yields carbometalation products and functionally substituted dimers and oligomers (Scheme 2,
Table 1). The resulting oligomers may be both functionally substituted organoaluminum
compounds (5, 6), as shown by mass-spectroscopic analysis of the deuterolysis products (11, 12),
and higher branched alkenes with a methylene double bond (7, 8). In this work, we mainly used
a small amount of MAO (40 equiv.) [13], [14]. This gives rise to organoaluminum derivatives (5,
6), which are subsequently oxidized to give methyl- or ethyl-substituted primary alcohols 9 and
10 containing 2 to 7 monomer units (Scheme 2). A higher content of MAO (200-250 equiv.) in
the L2ZrCl2-AlR3-MAO-alkene system results in the formation of α-olefin oligomers with a
terminal double bond (7 and 8).

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Scheme 2. Reaction of alkenes with AlR3 (R= Me, Et) in the presence of complexes 1-3 and
MAO.
n
n
9-I,a-c
9-II,a-c
10a-c
rac-1 (Y=C2H4 )
rac-2 (Y= SiMe2)
O2, H3O+
O2, H3O+
3
1-3, MAO
n
n
n
n
4a-c
R= Me (I), Et (II);
I,II
n=1-5
n=1-5
7-I,a-c
7-II,a-c
5-I,a-c
5-II,a-c
6-I,a-c
6-II,a-c
8a-c
R'= n-C4H9 (a), n-C6H13 (b), n-C8H17 (c)
D3O+
D3O+
n
n
n=1-5
n= 1-6
11-I,a-c
11-II,a-c
12a-c
1. BuLi
1. 3, AlMe3, MAO, 1 bar
n
2. O2, H3O+
2.Me3SiCl
n
(n= 1-10)
13
(n= 1-10)
10d
4d
1. BuLi
1. 2 or 3, AlEt3, MAO, 1 bar
n
2. O2, H3O+
2.Me3SiCl
n
(n= 1-10)
14
(n= 1-10)
9-IId
The reaction of alkenes 4a,b with AlMe3 in the presence of ansa-complex 1 and MAO
goes with high conversion of the substrate (98-99%) and provides mainly functionalized methyl-
substituted dimers and oligomers 5-Ia,b (n=2-6, totally 50-67%), functionalized dimers and
oligomers 6-Ia,b (n=2-6, totally 12-19%), carboalumination products 5-Ia,b (n=1, <11%) and
adducts 7-Ia,b with a methylene double bond (n=2-6, totally 15-25%) (Table 1, entries 1-4). The
reaction with 1-decene (4c) gives the same set of products, but runs with less conversion.
Table 1
Oligomerization of linear alkenes in the presence of complexes 1-3, AlR3 and MAO (molar ratio
[Zr]:[substrate]:[AlR3]:[MAO]=1:200:200:40, 72 h, 20С)
Entry
AlR3
Cata-
1-
Solvent Conversion
Mole ratio of productsa,b, %
5
6
7с
8
lyst Alkene
n
n
n
n
n
1
AlMe3
1
4a
CH2Cl2 99
1
2
3
4
5
6
1
11
7
7
20
10
6
3
3
10
4
3
3
5
3
1
3
2
toluene 99
1

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2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
1
2
3
4
1
2
3
4
5
1
2
3
1
2
3
4
5
1
2
3
4
1
2
1
2
3
4
1
2
3
1
2
3
1
2
3
4
5
6
12
13
13
12
11
10
7
12
14
13
10
10
22
18
15
7
5
11
8
9
5
4
7
8
3
4
2
3
3
6
7
6
6
3
4
4b
CH2Cl2 98
3
3
4
3
3
1
3
5
4
3
Toluene 99
8
5
3
2
1
2
1
5
6
7
4c
4b
4a
CH2Cl2 52
toluene 51
CH2Cl2 85
3
5
4
6
4
1
1
1
3
3
7
5
4
1
2
16
26
11
6
10
1
1
1
1
1
9
1
<1
8
9
Toluened 99
CH2Cl2 94
40
26
7
41
27
6
3
1
60
28
8
1
<1
6
2
1
17
7
3
2
1
-
3d
-
1
-
-
-
-
-
-
10
toluene 98
2
11
12
4b
4c
4a
CH2Cl2 92
toluene 80
64
18
10
27
7
1
67
7
7
3
1
1
20
6
6
1
CH2Cl2 95
Toluene 99
CH2Cl2 99
13
14
1
1
5
2
7
1
4
47
41
7
14
15
18
12
9
3
1
<1
<1
<1
15
AlEt3
1
2
1
3
5
3
2
6

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7
1
2
3
4
5
6
1
2
3
4
1
2
3
4
1
2
3
1
2
3
1
2
3
4
5
6
1
2
1
2
3
4
1
2
3
1
2
3
4
5
<1
36
32
14
6
2
16
toluene 99
2
2
1
<1
<1
3
17
18
4b
CH2Cl2 99
toluene 72
59
24
10
3
30
19
7
2
<1
13
3
19
20
21
4c
4a
4a
4b
CH2Cl2 90
toluene 40
toluene 99
61
13
3
11
7
8
3
<1
6
5
2
<1
4
<1
5
4
2
<1
23
20
20
13
11
54
30
4
39
14
4
35
20
4
2
1
1
1
1
22
23
3d
CH2Cl2 99
toluene 78
5
2
2
2
1
2
12
5
2
3
4
6
3
2
3
2
24
25
CH2Cl2 92
toluene 75
2
1
7
4
4
8
12
6
5
8
3
3
6
5
6
4
a Determined by GC of deuterolysis products.
bde% was determined by 13C NMR of products 9, 10.
cThe content of product 7 (n = 0) was <1%.
d 2 mol% of catalyst.
Dimethylsilylene bridged zirconocene catalyst 2 showed less activity in the reaction,
however, it possesses better selectivity towards the dimer 5-I (Table 1, entry 7).
The reaction of alkenes with AlMe3 in the presence of 40 equiv. of MAO and
conformationally mobile complex 3 involves high conversion of the substrate (80-99%) and
affords predominantly the carboalumination products (Table 1, entries 9-11,13). The replacement
of dichloromethane by toluene in this system increases the yield of 1-octene and 1-decene dimers
(entries 12, 14).
The using of AlEt3 in the studied reaction leads to ethyl-substituted alkene oligomers for
the whole range of tested catalysts and substrates. Ethyl-substituted functionalized derivatives 5-

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II (n=2-7) prevail in the case of conformationally rigid catalysts 1 and 2 (Table 1, entries 15-21).
Reaction, catalyzed by complex 3, goes with less selectively and gives a wider range of
oligomeric products (entries 22-25). It should be noted that addition of MAO to the catalytic
systems containing AlEt3 almost completely stops the cycloalumination pathway, which in the
absence of the activator is usually the main direction of the reaction [30]-[33]. The use of
dichloromethane as the solvent and either ansa-complex 1 or conformationally mobile complex
3 as the catalyst was found to result in the 92-99% conversion of the substrates and predominant
formation of carbometalation products 5-II (n=1, 35-61%) (Table 1, entries 17, 19, 22, 24),
whereas the chemoselectivity of the oligomer formation decreases. The replacement of
dichloromethane by toluene in these systems decreases the alkene conversion, but enhances the
chemoselectivity towards the formation of ethyl-substituted oligomers (entries 16, 18, 20, 21, 23,
25).
Alcohols 9, 10 obtained by oxidation and hydrolysis of products 5,6 formed in the reaction
of α-olefins with AlR3 catalyzed by complexes 1-3 and MAO were analyzed by mass
spectrometry and NMR spectroscopy. It was found that the reaction of alkenes with AlR3 in the
presence of conformationally rigid ansa-complexes 1 and 2 and MAO furnishes functionally
substituted dimers and oligomers with high diastereomeric purity of ~99% de. Thus, the 13С
NMR spectra of dimers 9-I obtained with the catalytic systems based on conformationally rigid
complexes 1 and 2 exhibit signals of one diastereomer (Fig. 10b, SI). The result is consistent
with published data on high stereoselectivity of ansa-complexes in alkene polymerization [5],
[6]. Unlike ansa-complexes, the use of conformationally flexible complex 3 as the catalyst leads
to the formation of functionally substituted oligomers 6 and 7 with up to five units, with dimers
being the predominant components and with low diastereoselectivity (not more than 5% de).
Indeed, the 13С NMR spectrum of compounds 9 I,II obtained after oxidation of the reaction
mixture shows doubled signals for the (RR+SS) and (RS+SR) diastereomers (Fig.10a, SI), which
attests to the loss of diaselectivity upon the insertion of a second alkene molecule into the
carbometallation product formed in the first stage of the reaction.
Thus, comparison of the conformationally mobile and rigid complexes demonstrates that
complexes with rigid geometry exhibit higher selectivity towards oligomerization. Moreover, the
use of ansa- complexes results in high process diastereoselectivity.
The reaction of propene (4d) with trialkylalanes in the presence of chosen catalysts 1-3 and
MAO affords functionally substituted oligomers with up to 11 units (Scheme 2).
Conformationally mobile complex 3 catalyzes the reaction of propene with AlMe3 at room
temperature in 24 h ([Zr]: [AlR3]:[MAO]=1:200:40, pressure of propene 1 bar) to give propene
oligomers 10d with the catalytic activity of 133 goligomer·molZr-1·h-1. Oligopropenes obtained in

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this reaction have an n-propyl starting group, as was also observed for the ansa-zirconocene-
MAO systems studied previously [7]-[9], indicating that the early stages of the process is
hydrometalation, which occurs due to the catalytically active sites containing a Zr-H bond
(Scheme 3). Conformationally rigid complexes 1 and 2 proved to be catalytically inert under the
same conditions. The replacement of AlMe3 by AlEt3 in the 5-L2ZrCl2-AlR3-MAO-alkene
systems makes it possible to perform propene oligomerization in the presence of ansa-complex
2, the catalytic activity of which is 340 goligomer ·molZr-1·h-1. The activity of complex 3 under these
conditions is lower, namely, 154 goligomer ·molZr-1·h-1. When propene reacts with AlEt3 in the
presence of complexes 2 and 3, the first stage is propene carbometalation, which is followed by
formation of substrate insertion products (9-II,d).
The 13С NMR of oxidized products 9-IId, 10d (Fig. 11, SI) and mass spectra of their
silylated derivativesError! Reference source not found. (Fig. 1) indicate the low
diastereoselectivity of the reactions catalyzed by complex 3, whereas high regio- and
diastereoselectivity are inherent to the catalytic system based on the zirconocenes with fixed
geometry (Fig. 1b).
The variety of products obtained in the studied reaction can be explained by the
mechanism presented in Scheme 3. Thus, the formation of Me(Et)-substituted oligomers 5 and 7
is due to the existence of active centers with a Zr-C bond, which carbometalate the alkenes
[15],[16], gradually increasing the oligomeric chain. The chain termination occurs as a result of
the transmetalation by AlR3 or due to the β-C-H activation providing hydrocarbons with a
methylene double bond. The latter process is a source of intermediates with an active Zr-H bond,
which hydrometalate the substrate and give products 6 and 8 with an n-alkyl starting group. It
should be noted as well that in systems with AlEt3, the addition of small amounts of MAO
probably reduced the rate of β-C-H activation, since we did not observe cyclomelation products,
for which a hydride transfer with ethane release and the formation of zirconacyclopropane is
required [33]; in addition, this fact is confirmed by a larger proportion of ethylated oligomers in
the reaction products.

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Fig. 1. Chromatogram of silylated derivatives 13,14: (a) reaction of AlMe3 with propene
catalyzed by complex 3; (b) reaction of AlEt3 with propene catalyzed by complex 2

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Scheme 3. Probable mechanism of reaction of alkenes with AlR3 (R= Me, Et) in the
presence of complexes 1-3 and MAO.
5
L2ZrCl2
AlR3
AlR3
AlR3
R= Me, Et
1-3
MAO
n
L2ZrRCl
L2
L2
AlEt3
Me(Et)- substituted oligomers,
Y - functional group
carbometalation
MAO
L2
L2
L2ZrEt2
-С2H6
7
cyclometalation
-C-H- activation
AlR3
AlR3
6
7
L2
hydrometalation
n
L2
H - substituted oligomers,
Y - functional group
-C-H- activation
8
If we consider diastereoselectivity, then in the case of conformationally flexible catalyst 3,
the subsequent insertion of substrate molecules into the carbometallation product is not
stereoselective (equal amounts of R and S): this means that the stereoselectivity of alkene
coordination is controlled via configuration of the catalytically active site to which the substrate
is coordinated (site control) rather than via the end group control (Scheme 4). For example, if А
and В are the possible conformers of the catalytically active sites produced by complex 3 [13],
the insertion of the first alkene molecule into the Zr-C bond proves to be faster than the transition
to another conformer: this accounts for good enantioselectivity of the methylalumination (up to
70%ее) [34]. The branched alkyl chain formed at zirconium apparently changes the rate of
transformation of one conformer to another (e.g., A to B), so that the rates of insertion of a
second molecule and ligand rotation become comparable; hence, the re and si coordinations of
the alkene are equally probable. In the case of the complex with the fixed geometry (С, Scheme
4), the conformational transition is impossible; this accounts for high diastereoselectivity of the
dimerization and oligomerization.

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Scheme 4. Conformational mobility of ligands in complexes 1-3 and
diastereoselectivity of alkene insertion.
R
S
R
R
S
re
si
A
R
R
R
R
R
si
re
B
R
R
S
R
S
re
re
C
4. Conclusions
In a study of the reaction between terminal alkenes and AlR3 (R = Me, Et) in the presence of
chiral Zr complexes, rac-[Y(η5-C9H10)2]ZrCl2 (Y = C2H4, SiMe2) or (NMI)2ZrCl2 (NMI- η5–
neomenthylindenyl), the conditions that provide chemo- and diastereoselective formation of
functionally substituted oligomers were found. Comparison of the catalysts showed that
complexes with rigid geometry possess higher selectivity towards oligomerization, whereas
conformationally flexible complex provides carbometalation products to a greater extent.
Moreover, the use of ansa- complexes results in high process diastereoselectivity. Thus, we
showed the possibility of using Ziegler-Natta type catalytic systems for one-pot
diastereoselective synthesis of functionally substituted linear alkene dimers and propene
oligomers. This strategy could be subsequently used for the synthesis of a broad range of chiral
stereoregular molecules suitable as building blocks for the preparation of biologically active
compounds.
Acknowledgements

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The authors thank the Russian Foundation of Basic Research (Grants No. 16-33-
60203mol_a_dk, 18-03-01159a) for financial support.
Supplementary data to this article can be found online at

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Graphical Abstract

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Highlights
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Reaction of alkenes with AlR3 (R = Me, Et) catalyzed by chiral Zr complexes and MAO was studied
Ansa- zirconocenes with rigid geometry possess high chemo- and diastereoselectivity
Diastereomerically pure functionalized alkene dimers and propene oligomers were obtained