Room temperature highly enantioselective nickel-catalyzed hydrovinylation

Article abstract of DOI:10.1002/adsc.200900559

At room temperature, nickel catalysts based on the new phosphoramidite (11bR)-N-[(S)-1-(naphthalen-1-yl)ethyl]-N-[(S)-1-(naphthalen-2-yl)ethyl] dinaphtho[2,1-d:1, 2'-f] [1,3,2]dioxaphosphepin-4-amine provide excellent selectivities for 3-arylbut-1-enes (9

Full text of DOI:10.1002/adsc.200900559

COMMUNICATIONS
DOI: 10.1002/adsc.200900559
Room Temperature Highly Enantioselective Nickel-Catalyzed
Hydrovinylation
Nicolas Lassauque,a Giancarlo Franciꢀ,a,* and Walter Leitnera,*
a
Institut fꢁr Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 1, 52074 Aachen,
Germany
Fax : (+49)-241-80-22177; e-mail: francio@itmc.rwth-aachen.de or leitner@itmc.rwth-aachen.de
Received: August 7, 2009; Published online: December 8, 2009
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.200900559.
Abstract: At room temperature, nickel catalysts
based on the new phosphoramidite (11bR)-N-[(S)-
1-(naphthalen-1-yl)ethyl]-N-[(S)-1-(naphthalen-2-
yl)ethyl]dinaphtho[2,1-d:1’,2’-f]
ACHTUNGERTN[NUNG 1,3,2]dioxaphosphe-
ACHTUNGTRENNUNGpin-4-amine provide excellent selectivities for 3-ar-
ylbut-1-enes (93–99%) with high enantioselectivities
(90–95% ee) and TOFs (up to 8300 hÀ1) in the hy-
drovinylation of electron-rich and electron-poor vi-
nylarenes. Within a few minutes, useful chiral build-
ing blocks and intermediates can be synthesized
using this practical catalytic system.
Figure 1. Benchmark phosphoramidite ligands for the Ni-
catalyzed hydrovinylation.
À
Keywords: asymmetric catalysis; C C coupling;
olefin dimerization; phosphoramidite ligands
NaBArF as the activator, resulted in a very active and
highly selective catalytic system at À708C, but only
moderate chemo- and enantioselectivity were ob-
The nickel-catalyzed heterodimerization of an olefin served at higher temperature.[4a] Since then, ligand 1
with ethylene (hydrovinylation) was one of the first and related phosphoramidites have been successfully
examples of asymmetric catalysis ever reported.[1,2] applied to other substrates under similar conditions.[5]
Since this first pioneering study, major progress in this As shown by a combination of experimental and com-
atom-efficient reaction has been achieved with the in- putational studies,[8] a phenyl ring from the NCH-
troduction of the unique Wilke ligand in the 1980s[3]
ACHTUNGTRENUN(GN CH3)Ph side arm of 1 acts as a hemilabile donor in
and of modular phosphoramidite ligands more recent- some intermediates of the catalytic cycle[9,10] and is de-
ly.[4,5] Although several protocols are known providing cisive for both the catalyst activity and enantioselec-
the desired chiral 3-arylbut-1-enes in high yields and tivity.[8] Indeed, the presence of at least one 1-(ar-
enantioselectivities, all of them require the reaction to
ACHTUNGTRENyNGNU l)ethyl group at the nitrogen guaranteed enhanced
be carried out at very low temperature (typically enantioselectivity in ligand frameworks as diverse as
À788C).[6,7] This hampers a widespread application of azaphospholenes,[3] phosphoramidites,[4a,5] and phos-
this useful coupling reaction. We disclose here readily phorous triamides.[11] Recently,[12] Smith and RajanBa-
accessible chiral ligands which for the first time bu applied ligand 2 (Figure 1) bearing an N-benzyl-1-
enable highly enantioselective Ni-catalyzed hydro- (1’-naphthyl)ethylamine moiety in the Ni-catalyzed
A
hydrovinylation of various substrates at À788C with
led to the highly chemo- and enantio-selective Ni-cat- strate only a minor depletion of the enantioselectivity
alyzed hydrovinylation of styrenes at low tempera- was observed by raising the temperature from À788C
ture. In particular, the Feringa ligand 1 (Figure 1), to- to 08C (96% and 92%, respectively).[12b]
gether with the metal precursor [(allyl)NiCl]2 and
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Nicolas Lassauque et al.
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To study the role of the aryl group at the a-position
to the nitrogen more systematically, we set out to ex-
plore the Ni-catalyzed hydrovinylation with all three
possible combinations of (R)-binaphthol-based phos-
phoramidites comprising two chiral (S)-1-(naph-
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNGthyl)ethyl-(S)-1-(2’-naphthyl)ethylamine (5), respec-
tively (Figure 2). Ligands 3[13] and 4[14] were prepared
accordingly to literature procedures, while the new
ligand 5 was synthesized starting from (S)-1-(1’-naph-
thyl)ethylamine as shown in Scheme 1 (see Support-
ing Information for full experimental details).[15]
Scheme 2. Asymmetric hydrovinylation: substrates, ligands
and activators used in this study.
the synthesis of the anti-inflammatory drugs Naprox-
enꢃ and Ibuprofenꢃ, respectively,[3,12b,18] and p-bromo-
AHCTUNGTREGsNNUN tyrene (6d) as an example for an electron-poor sub-
strate (Scheme 2). Representative results of this study
are summarized in Table 1.
When the catalyst system based on ligand 3 was ap-
plied in the hydrovinylation of styrene under standard
conditions at À708C no significant conversion was ob-
served. Even at 08C, only 40% conversion, very low
chemo- (20%) and enantioselectivity (15%) were ob-
tained, indicating that 3 is a poor ligand for this reac-
tion. In sharp contrast, the isomeric ligand 4 forms an
active and highly selective hydrovinylation catalyst.
At a 6a/Ni ratio of 250 and À708C, almost all of the
substrate was selectively converted within 40 min into
3-phenylbut-1-ene (7a) with an ee of 97%, using
either NaBArF or InI3 as activator (entries 1 and 2).
Even higher enantioselectivities were achieved with
ligand 5. Under standard conditions, almost perfect
enantioselectivity was obtained in the hydrovinylation
of styrene (99% ee with NaBArF, 98% ee with InI3,
entries 3 and 4). Thus, while the presence of a bis-
(S,S)-[1-(1’-naphthyl)ethyl]amine group in 3 almost
Figure 2. Phosphoramidite ligands used in this study.
The pre-catalysts were formed mixing [(allyl)NiBr]2 inhibits the catalytic cycle, the subtle modification
with two equivalents of the phosphoramidites 3–5 in from 1-naphthyl to 2-naphthyl of both or even one
CH2Cl2 for 10 min. Catalyst activation was carried out aryl moiety in 4 and in 5, respectively, is sufficient
with NaBArF {BArF=B
(CF3)2-C6H3]4}[16] or with and crucial for gaining activity and selectivity as well.
ACHUTGTNRENNUG[3,5-ACHTUTGNRENNUGN
InI3.[17] The new catalytic systems were evaluated in
Similar high levels of enantioselectivity were ob-
the hydrovinylation of the benchmark substrate sty- tained with ligand 4 also in the hydrovinylation of the
rene (6a), 6-methoxy-1-vinylnaphthalene (6b) and p- other substrates 6b, 6c and 6d with ees ranging from
isobutylstyrene (6c), which can serve as precursors for 94% to 99% (entries 5, 6, 9, 13, and 14). Selectivities
Scheme 1. Synthesis of ligand 5.
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Room Temperature Highly Enantioselective Nickel-Catalyzed Hydrovinylation
Table 1. Representative results of the asymmetric Ni-catalyzed hydrovinylation of vinylarenes with ligand 4 and 5.[a]
COMMUNICATIONS
[b]
Entry Substrate Activator Ligand Substrate/
[Ni]
T
t
Conversion
Selectivity for 7
[%]
ee (7)
[%]
TOFav
[hÀ1]
[8C] [min] [%]
1
2
3
4
6a
6a
6a
6a
6b
6b
6b
6b
6c
NaBArF
InI3
NaBArF
InI3
NaBArF
InI3
NaBARF 5
4
4
5
5
4
4
250
250
250
250
125
125
125
125
250
250
250
250
250
250
250
250
1000
1000
1000
1000
250
250
250
250
1000
1000
À70 40
À70 40
À70 40
À70 40
À70 120
À70 120
À70 120
À70 120
À70 15
À70 15
À70 150
À70 150
À70 30
À70 30
À70 30
À70 30
97
97
90
>99
>99
>99
>99
>99
40
>99
>99
99
97 (S)
97 (S)
99 (S)
98 (S)
99 (S)
99 (S)
370
370
340
>380
>62
>62
99
5[c]
6[c]
7[c]
8[c]
9[d]
>99
>99
>99
>99
96
99
80
90
>99
98
>99 (S) >62
>99 (S) >62
InI3
5
4
5
4
5
4
4
5
5
5
5
5
5
5
5
5
5
5
5
NaBArF
NaBArF
NaBArF
NaBArF
NaBArF
InI3
NaBArF
InI3
NaBArF
InI3
NaBArF
InI3
NaBArF
InI3
NaBArF
InI3
NaBArF
InI3
95 (S)
96 (S)
95 (S)
96 (S)
96 (S)
94 (S)
98 (S)
97 (S)
96 (S)
95 (S)
93 (S)
90 (S)
95 (S)
94 (S)
90 (S)
89 (S)
92 (S)
90 (S)
400
340
10[d] 6c
11[d] 6c
12[d] 6c
34
>99
>99
95
99
99
>99
82
>99
98
>100
>100
477
>500
>500
>500
1640
>2000
3450
2520
>3125
>3125
>8300
>5000
2790
13
14
15
16
17
18
6d
6d
6d
6d
6a
6a
99
>99
>99
99
98
99
94
93
95
92
0
30
30
17
20
5
0
19[e] 6a
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
20
6a
6b
6b
84
21[f]
22[f]
>99
>99
>99
>99
93
5
2
3
30
30
23[d] 6c
24[d] 6c
25
26
6d
6d
95
95
76
2280
[a]
[b]
[c]
[d]
[e]
[f]
Reaction conditions: [(allyl)LNiBr]=0.012 mmol, activator=1 equiv., CH2Cl2 =3 mL.
Turnover frequency for conversion of 6.
CH2Cl2 =10 mL.
Reaction conditions: [(allyl)LNiBr]=0.006 mmol, activator=1 equiv., CH2Cl2 =1.5 mL.
Isolated yield 83%.
CH2Cl2 =5 mL.
for the desired products 7b–d were typically very high (entry 17), which are the highest values obtained for
(>99%) and a slight decrease was observed upon this transformation under these conditions.[21] Similar
complete substrate consumption only for 6c selectivities and higher activity were observed with
(entry 11).[19] The catalyst performances achieved InI3 as activator under the same conditions (entry 18).
upon activation with NaBArF and with InI3 are large- Finally, these excellent levels of chemo- and enantio-
ly identical, confirming the efficiency of this Lewis selectivities could be retained even by carrying out
acid for activation (cf. entries 5/6 and 13/14).[17] Again, the reaction at room temperature (entries 19–26).
even higher enantioselectivities coupled with chemo- Standard work-up provided essentially pure products
selectivities ꢀ99% have been obtained under the in high yields (see Experimental Section for details).
same conditions with ligand 5. To the best of our
With NaBArF activation, the desired products were
knowledge, the enantiomeric excesses achieved with 5 obtained with chemoselectivities between 94% and
are at the same excellent level (for 6b and 6c, en- 97% and enantioselectivities between 90% and 95%.
tries 7 and 10, respectively) or even surpass (for 6a Moreover, extremely high TOFs ranging from 2790 to
and 6d, entries 3 and 15, respectively) the highest ees >8300 hÀ1 were observed under these conditions.
reported so far for these substrates.[2,20]
Comparable results were achieved again upon catalyst
Encouraged by the extremely high selectivities ob- activation with InI3 (chemoselectivities 92%–99%, ees
tained at low temperature, we carried out the hydro- 89%–94%).[22] Thus, product 7b, which is a possible
vinylation of styrene in the presence of 5 at higher precursor for Naproxenꢃ, was obtained within 5 min
temperature. At 08C almost full conversion, perfect in 94% GC yield and 95% ee by simply keeping
chemoselectivity (>99%) and an enantioselectivity of under ethylene atmosphere a CH2Cl2 solution of 6b
96% were achieved upon activation with NaBArF and the catalyst components without external temper-
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Nicolas Lassauque et al.
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6.7–8.6 (14H, m), 10.74 (1H, br), 10.86 (1H, br); 13C NMR
(100 MHz, CDCl3): d=21.03 (CH3), 22.02 (CH3), 51.50
(CH), 51.47 (CH), 121.53 (CarH), 124.77 (CarH), 125.63
(CarH), 125.95 (CarH), 126.23 (CarH), 126.33 (CarH), 126.35
(CarH), 126.74 (CarH), 127.63 (CarH), 128.16 (CarH), 128.86
(CarH), 128.88 (CarH), 129.21 (CarH), 129.39 (CarH), 130.33
(Car), 132.86 (Car), 132.95 (Car), 133.11 (Car), 133.42 (Car),
133.69 (Car); HR-MS (EI): m/z=325.18277, calcd. for
C24H23N: 325.18250; [a]2D0: 114.31 (c 0.8, CH2Cl2).
ature control (entry 21). Product 7c, providing access
to Ibuprofenꢃ, was formed in less than 2 min in 95%
GC yield and 90% ee (entry 23).
In summary, the subtle interplay of the steric bulk
and hemilabile interaction of the naphthyl groups at
the a-position to the nitrogen strongly controls the ef-
ficacy of the isomeric ligands 3–5. Especially with the
readily accessible ligand 5, the hydrovinylation can
now be carried out in a very simple protocol at room
temperature to convert electron-rich and electron-
poor substrates rapidly to chiral products in high
yields and enantioselectivities. This further substanti-
ates the role of hydrovinylation as a valuable and
practical addition to the still limited tool box of asym-
Synthesis of (11bR)-N-[(S)-1-(naphthalen-1-yl)ethyl]-
N-[(S)-1-(naphthalen-2-yl)ethyl]dinaphtho[2,1-d:1’,2’-
f]ACTHNUTRGNEUNG
[1,3,2]dioxaphosphepin-4-amine (5)[15]
Et3N (2.1 g, 20.8 mmol) was added at 08C through a septum
to a solution of PCl3 (0.571 g, 4.16 mmol) in CH2Cl2 (6 mL).
After 5 min, compound 8 (1.5 g, 4.16 mmol) was added neat
in one portion and the reaction mixture was stirred for
10 min at 08C and then for 5 h at room temperature. (R)-
1,1’-Binaphthyl-2,2’-diol (1.19 g, 4.16 mmol) was added as a
solid in one portion to the reaction mixture at 08C and the
suspension was stirred overnight at room temperature. The
solvent was evaporated under reduced pressure. The yellow
solid residue was dissolved in CH2Cl2 (5 mL) and filtered
through a filter-cannula. The remaining solid residue was ex-
tracted twice with CH2Cl2 (2 mL). The combined solutions
were evaporated under reduced pressure and the residue
was purified by column chromatography on silica gel (hex-
À
metric C C coupling reactions.
Experimental Section
General Remarks
All manipulations were carried out under argon using
Schlenk-tube techniques. NaBArF,[23] [(h3-allyl)NiBr]2,[24]
ligand 3,[13] ligand 4[13] and compound 6c[25] were prepared
according to literature procedures. InI3 was provided by
Acros Organics. 1-Acetylnaphthalene and 2-acetylnaphtha-
lene were provided by Aldrich and used without further pu-
rification. (S)-1-(1’-Naphthyl)ethylamine and (S)-1-(2’-naph-
thyl)ethylamine were provided by BASF and used without
further purification.
AHCTUNGRTENaNGUN ne:CH2Cl2 =4:1) to obtain pure 5; yield: 1.2 g (45%).
1H NMR (600 MHz, CDCl3): d=1.90 (6H, br), 4.97 (1H,
br), 5.60 (1H, br), 7.16–8.08 (26H, m); 13C NMR (150 MHz,
CDCl3): d=21.18 (CH3), 24.29 (CH3), 49.65 (CH), 52.50
(CH), 121.82 (Car), 122.39 (CarH), 122.56 (CarH), 122.79
(CarH), 124.24 (Car), 124.45 (CarH), 124.55 (CarH), 124.80
(CarH), 124.89 (CarH), 124.95 (CarH), 125.24 (CarH), 125.28
(CarH), 125.38 (CarH), 125.75 (CarH), 126.08 (CarH), 126.14
(CarH), 126.79 (CarH), 127.00 (CarH), 127.21 (CarH), 127.22
(CarH), 127.26 (CarH), 127.32 (CarH), 127.73 (CarH), 128.22
(CarH), 128.39 (Car), 128.41 (CarH), 128.43 (CarH), 129.64
(CarH), 130.47 (CarH), 130.51 (Car), 131.50 (Car), 132.07 (Car),
132.52 (Car), 132.89 (Car), 132.97 (Car) 133.33 (Car), 139.19
(Car), 139.77 (Car), 149.63 (Car), 150.36 (Car); 31P{1H}
NMR spectra were measured at room temperature with a
Bruker AV-400 or a Bruker AV-600 spectrometer. Chemical
shifts are given relative to TMS by using the solvent signals
1
as internal reference for H as well as 13C NMR and H3PO4
(85%) as external reference for 31P NMR spectroscopy.
Mass spectra (EI) were recorded on a Finnigan MAT 95
and optical rotations on a Jasco P-1020 polarimeter.
Synthesis of (S)-1-(1’-Naphthyl)ethyl-(S)-1-(2’-
naphthyl)ethylammonium Chloride (9)[15]
(243 MHz, CDCl3):
d = 145.68; HR-MS (EI): m/z=
A mixture of 2-acetylnaphthalene (2.926 g, 17.19 mmol),
(S)-1-(1-naphthyl)ethylamine (2.94 g, 17.19 mmol) and tita-
nium(IV) isopropoxide (22 mL, 72.6 mmol) in ethyl acetate
(10 mL) was stirred for 30 min at room temperature. Then,
10% palladium on charcoal (90 mg, 0.5 mol%) was added
and the mixture stirred overnight at room temperature
under hydrogen (1 bar). An aqueous solution of sodium hy-
droxide (1M, 50 mL) was then added to the mixture. After
stirring for 10 min, the solution was filtered and the solid
washed with ethyl acetate (3ꢄ20 mL). The organic layer
was separated. The aqueous phase was extracted with ethyl
acetate (3ꢄ 20 mL). The combined organic phase was dried
over Na2SO4 and the solvent evaporated under reduced
pressure. A colourless oil was obtained, which was dissolved
in an ethyl acetate/methanol mixture (75:25). A solution of
HCl (1M) was added dropwise until pH 1 was reached. The
solution was then placed at À188C overnight. White crystals
of the diastereomerically pure compound 9 formed; yield:
639.23244, calcd. for C44H34O2NP: 639.23217. [a]2D0: À216.88
(c 0.9, CH2Cl2).
General Procedures for the Hydrovinylation
Reactions
Pre-catalyst preparation: Pre-catalysts [(h3-allyl){(Ra ,SC ,SC)-
4}NiBr] (9) and [(h3-allyl){(Ra ,SC,SC)-5}NiBr] (10) were pre-
pared by mixing in CH2Cl2 (5 mL) at 08C for 10 min the
complex [(h3-allyl)NiBr]2 (56.2 mg, 0.156 mmol) with the
ligand (Ra ,SC ,SC)-4 or (Ra ,SC ,SC)-5 (200 mg, 0.312 mmol),
respectively. After evaporation of the solvent under reduced
pressure, an orange powder was obtained in both cases,
which was used without further purification.
Hydrovinylation of styrene 6a at À708C (Table 1, entries 3
and 4): A solution of pre-catalyst 10 (9.8 mg, 0.012 mmol)
and styrene 6a (0.35 mL, 3 mmol) in CH2Cl2 (3 mL) was
cooled to À708C using a dry-ice/i-PrOH bath. The cold solu-
tion was then transferred via syringe to a Schlenk flask con-
1
3.0 g (49%). H NMR (400 MHz, CDCl3): d=1.96 (3H, d,
J=6.9 Hz), 2.03 (3H, d, J=6.9), 4.12 (1H, m), 4.76 (1H, m),
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Room Temperature Highly Enantioselective Nickel-Catalyzed Hydrovinylation
COMMUNICATIONS
taining the activator NaBArF (10.3 mg, 0.012 mmol) or InI3
(5.6 mg, 0.012 mmol) at the same temperature. The resulting
yellow mixture was allowed to warm to 08C for three mi-
nutes and then the now dark red solution was cooled down
again to À708C. The reaction was started by exchanging the
inert gas for ethylene by bubbling it through the solution for
5 s and keeping the Schlenk flask under an ethylene atmos-
phere at ambient pressure during the reaction. After 40 min,
the catalyst was quenched with a solution of NH3 (20% w/w,
1 mL). Ethylbenzene (0.4 mL, 3 mmol) was added as inter-
nal standard for the GC analysis and the solution was al-
lowed to warm up to room temperature. The organic phase
was separated, dried over Na2SO4, filtered through a pad of
silica and analyzed via GC.
Hydrovinylation of styrene 6a at 08C (Table 1, entry 17
and 18): The same procedure was followed as above except
that both activation and reaction were performed at 08C.
Hydrovinylation of styrene 6a at room temperature
(Table 1, entry 19): A solution of pre-catalyst 10 (9.8 mg,
0.012 mmol) and styrene 6a (1.40 mL, 12 mmol) in CH2Cl2
(3 mL) was added via syringe to a Schlenk flask containing
the activator NaBArF (10.3 mg, 0.012 mmol). The reaction
was started by exchanging the inert gas for ethylene by bub-
bling it through the solution for 5 s and keeping the Schlenk
flask under an ethylene atmosphere at ambient pressure
during the reaction. After 17 min, the catalyst was quenched
with a solution of NH3 (20% w/w, 1 mL). The organic phase
was separated and the aqueous phase washed with CH2Cl2
(3ꢄ2 mL). The combined organic phases were dried with
Na2SO4, filtered and the solvent removed with a rotary
evaporator to give a yellowish liquid. This liquid was passed
through a short silica column (eluent n-pentane) and the sol-
vent removed with a rotary evaporator affording pure prod-
uct 7a as a colourless liquid; yield: 1.31 g (83%).
Chem. Soc. 2006, 128, 2780; d) B. Saha, C. R. Smith,
T. V. RajanBabu, J. Am. Chem. Soc. 2008, 130, 9000.
[6] Only in the case of less reactive substrates like a-alkyl-
vinyl-arenes, can the hydrovinylation be performed at
room temperature with high selectivity: W.-J. Shi, Q.
Zhang, J.-H. Xie, S.-F. Zhu, G.-H. Hou, Q.-L. Zhou, J.
Am. Chem. Soc. 2006, 128, 2780.
[7] For examples of hydrovinylation at room temperature
or above giving high chemo-, but no or only moderate
enantioselectivity, see [Ni]: a) Q. Zhang, S.-F. Zhu, X.-
C. Qiao, L.-X. Wang, Q.-L. Zhou, Adv. Synth. Catal.
2008, 350, 1507; [Ru]: b) C. S. Yi, Z. He, D. W. Lee, Or-
ganometallics 2001, 20, 802; c) R. P. Sanchez, B. T. Con-
nell, Organometallics 2008, 27, 2902; [Co]: d) M. M. P.
Grutters, C. Muller, D. Vogt, J. Am. Chem. Soc. 2006,
128, 7414.
[8] M. Hçlscher, G. Franciꢀ, W. Leitner, Organometallics
2004, 23, 5606.
[9] For an oxygen donor acting as hemilabile functional
groups in hydrovinylation catalysts see: a) N. Nomura,
J. Jin, H. Park, T. V. RajanBabu, J. Am. Chem. Soc.
1998, 120, 459; b) M. Nandi, J. Jin, T. V. RajanBabu, J.
Am. Chem. Soc. 1999, 121, 9899; c) J. Joseph, T. V. Ra-
janBabu, E. D. Jemmis, Organometallics 2009, 28, 3552.
[10] The intramolecular coordination of a phenyl group of 1
in Pd, Pt, Rh and Ru complexes was experimentally
confirmed in solution via NMR spectroscopy and in the
solid state: a) I. S. Mikhel, H. Rꢁegger, P. Butti, F.
Camponovo, D. Huber, A. Mezzetti, Organometallics
2008, 27, 2937; b) S. Filipuzzi, P. S. Pregosin, M. J. Cal-
horda, P. J. Costa, Organometallics 2008, 27, 2949.
[11] K. Barta, M. Hçlscher, G. Franciꢀ, W. Leitner, Eur. J.
Org. Chem. 2009, 4102.
[12] a) C. R. Smith and T. V. RajanBabu, Org. Lett. 2008,
10, 1657; b) C. R. Smith and T. V. RajanBabu, J. Org.
Chem. 2009, 74, 3066.
Acknowledgements
[13] L. A. Arnold, R. Imbos, A. Mandoli, A. H. M. de Vries,
R. Naasz, B. L. Feringa, Tetrahedron 2000, 56, 2865.
[14] H. Hꢅnon, M. Mauduit, A. Alexakis, Angew. Chem.
2008, 120, 9262; Angew. Chem. Int. Ed. 2008, 47, 9122.
[15] Synthetic procedure adapted from: a) A. Alexakis, S.
Gille, F. Prian, S. Rosset, K. Ditrich, Tetrahedron Lett.
2004, 45, 1449; b) D. Polet, A. Alexakis, K. Tissot-
Croset, C. Corminboeuf, K. Ditrich, Chemistry 2006,
12, 3596.
We thank Mrs. H. Eschmann (ITMC) for the GC and HPLC
measurements, Prof. K. Ditrich (BASF) for a generous gift of
chiral amines, and the Deutsche Forschungsgemeinschaft for
financial support (project CALAPAI, FR2487/1-1).
References
[16] N. Nomura, J. Jin, H. Park, T. V. RajanBabu, J. Am.
Chem. Soc. 1998, 120, 459.
[17] N. Lassauque, G. Franciꢀ, W. Leitner, Eur. J. Org.
Chem. 2009, 3199.
[18] V. Fassina, C. Ramminger, M. Seferin, A. L. Monteiro,
Tetrahedron 2000, 56, 7403.
´
[1] B. Bogdanovic, Adv. Organomet. Chem. 1979, 17, 105.
[2] a) P. W. Jolly, G. Wilke, in: Applied Homogeneous Cat-
alysis with Organometallic Compounds (Eds.: B. Cor-
nils, W. A. Herrman), VCH, New York, 1996, Vol. 2,
p 1024; b) for a recent review on hydrovinylation see:
T. V. RajanBabu, Synlett 2009, 6, 853.
[19] A reduced chemoselectivity is sometimes observed
when no more substrate is present in the reaction mix-
ture, as the primary product can undergo consecutive
reactions like isomerization and oligomerization. These
side reactions are more pronounced in the presence of
palladium catalysts: see, e.g., W. H. Shi, J. H. Xie, Q. L.
Zhou, Tetrahedron: Asymmetry 2005, 16, 705–710.
[20] Highest reported enantiomeric excess: 6a 95%
(ref.[3,4a]); 6b 99% (ref.[12a]); 6c 97% (ref.[12a]); 6d 92%
(ref.[4a]).
[3] G. Wilke, Angew. Chem. 1988, 100, 189; Angew. Chem.
Int. Ed. Engl. 1988, 27, 185.
[4] a) G. Franciꢀ, F. Faraone, W. Leitner, J. Am. Chem.
Soc. 2002, 124, 736; b) C. J. Diez-Holz, C. Bçing, G.
Franciꢀ, M. Hçlscher, W. Leitner, Eur. J. Org. Chem.
2007, 2995.
[5] a) R. Kumareswaran, M. Nandi, T. V. RajanBabu, Org.
Lett. 2003, 5, 4345; b) A. Zhang, T. V. RajanBabu, J.
Am. Chem. Soc. 2006, 128, 54; c) W.-J. Shi, Q. Zhang,
J.-H. Xie, S.-F. Zhu, G.-H. Hou, Q.-L. Zhou, J. Am.
Adv. Synth. Catal. 2009, 351, 3133 – 3138
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
3137

Nicolas Lassauque et al.
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[21] For comparison, 76% ee and a chemoselectivity of 78%
were obtained with ligand 1 at 08C (ref.[4a]).
[22] We noted a tendency for oligomerization of the sub-
strates when the ratio InI3/[Ni] exceeds one, which is
not the case, however, at low temperature.
[23] N. A. Yakelis, R. G. Bergman, Organometallics 2005,
24, 3579; M. Brookart, B. Grant, A. F. Volpe, Organo-
metallics 1992, 11, 3920.
[24] M. Brookhart, E. Hauptman, WO Patent 98/22424,
1998.
[25] S. Ohsugi, K. Nishide, M. Node, Tetrahedron 2003, 59,
1859.
3138
asc.wiley-vch.de
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2009, 351, 3133 – 3138