Asymmetric Organometallic Catalysis

Transcription

Asymmetric Organometallic Catalysis
J.-P. Genet, V. Michelet, V. Vidal
Laboratoire de Synthèse Sélective Organique et Produits Naturels – UMR CNRS 7573
E.N.S.C.P. - 11 Rue P. & M. Curie – 75231 PARIS Cedex 05
[email protected] ; [email protected] ; [email protected]
1 - Introduction
Asymmetric catalysis has become one of the most powerful methods to produce a
single-enantiomer drug and now provides one of the most cost-effective and
environmentally responsible methods for the production of a vast array of structurally
diverse, enantiomerically pure compounds. Since a small amount of chiral catalyst can, in
principle, produce a large amount of optically active product. Transition metal
enantioselective catalysis is certainly among the most challenging and widely
investigated area in modern organometallic chemistry. In 1971, H. B. Kagan and T. P.
Dang discovered the Diop ligand or (2,3-O-isopropylidene)-2,3-dihydroxy-1, 4-bis
(diphenylphosphino)butane[1],
the
first
C2-symmetric
diphosphane
that
allowed
asymmetric hydrogenation of dehydroamino acids , when complexed with rhodium. The
basic idea was that a suitable functionality and skeletal rigidity of the phosphine ligand
would contribute to the differentiation of transition states needed to accomplish
enantioselective
catalysis.
The
rhodium
(I)-DIOP
catalyst
was
superior
to
monophosphines catalysts in asymmetric hydrogenation of dehydro amino acids. It is
interesting to note that Pr. H. B. Kagan's 1970 initial patent also includes the structure
of an atropisomeric ligand, a potential candidate for asymmetric catalysis, which is now
developed by Roche under the name Biphemp.
This new idea showed that the chirality of phosphorous atom wasn't necessary to obtain
good selectivity, complex rigidity between the metal and the bidentate ligand allowed a
better discrimination of the transition states needed to achieve an efficient
asymmetric catalysis. This concept, using Rh-dipamp as catalyst unable Monsanto to be
Catalysis in France: an Adventure
2007, July
1 / 30
the primary supplier of L-DOPA, a compound used in the stabilizing the effects of
Parkinson's disease[2]. Numerous C2 symmetric ligands have since been described, the
best example being the Binap, synthesized ten years after by the team of R. Noyori and
H. Takaya[3]. This master discovery generated intense activity in the new field of
asymmetric catalysis. H. B. Kagan, in collaboration with C. Agami have made another
important discovery when they revealed the non-linear effects of asymmetric
catalysis[4-6]. The present article contains some French contributions in the field
asymmetric catalysis.
2 - Asymmetric Hydrogenation
Following Wilkinson's work[7] on alkene's hydrogenation with the complex RhCl(PPh3)3, L.
Horner[8] and W. S. Knowles[9] teams, showed that with the replacement of
triphenylphosphane by a chiral monophosphane, the hydrogenation of atropic acid led to
a low 15% enantioselectivity. The first meaningful results in asymmetric hydrogenation
(63% ee) came from the H.B. Kagan team using the bidentate chiral ligand Diop
associated with a rhodium complex. The first enantioselective hydrogenation of
dehydroamino acids using the Diop ligand as chiral ligand[10], have also been described.
The realization of meaningful enantioselectivity with the Diop ligand was a great
breakthrough in the field of asymmetric hydrogenation.
Ph
COOH
[Rh] cat.
(R,R)-DIOP
Ph
COOH
H
H2 (1.1 atm)
95%, 63% ee
O
PPh2
PPh2
O
R
AcNH
[Rh] cat.
(R,R)-DIOP
H
CH2R
AcNH
COOH H2 (1.1 atm)
H
(R,R)-DIOP
COOH
R=H, 95%, 73% ee
R=Me, 90%, 82% ee
Numerous
examples
of
asymmetric
catalytic
reduction
such
as
enamides
hydrogenation[11], and the imines hydrosilylation[12], have been realized using the Diop
ligand and a rhodium complex[13]. In 1973 the Diop ligand was linked on a Merrifield
resin. It was the first example of solid supported asymmetric catalysis[14]. H.B. Kagan
and his collaborators studied the asymmetric reduction of original substrates such as
mono-dehydropeptides[15], mono-dehydroenkephalines[16] and bis-dehydrodipeptides[17]
2007, July
2 / 30
with excellent diastereoselectivities. After the Diop ligand, the Orsay team turned to
the synthesis of other types of original ligand. They designed Diop ligand analogues[18]
which are efficient in both hydrogenation and hydrosilylation. The synthesis of
Phellanphos, Nopaphos[19] or Norphos analogues such as 6-endo-hydroxy Norphos[20] and
its acyclic analogue[21] have been realized and their properties in catalysis have been
assessed. A general synthesis of 2-hydroxyalkyl diphenylphosphanes has been
described[22] as well as the synthesis of a multidentate ligand[23].
Following
these
pioneer
discoveries,
enantioselective
hydrogenation
through
homogenous catalysis has become a core technology to generate stereogenic tertiary
carbon. J.-C. Fiaud's team evaluated the catalytic activity of chiral 2,5-disubstituted
phospholanes
as
ligand
for
rhodium-catalyzed
asymmetric
hydrogenation
of
dehydroamino acids[24]. The hydrogenation of (Z)-N-acetamidocinnamate methyl yielded
up
to
93%
enantioselectivity[24].
of
Chiral
1,2,5-triphenylphospholanium
tetrafluoroborate salt[24], chiral secondary diphenylphospholane[24] and a series of
enantiopure phosphinites were synthesized and used in asymmetric hydrogenation of
functionalized alkenes[24].
CO2Me [Rh] cat., / L*
Ph
NHAc
H2
Ph
CO2Me
H
NHAc
L* = Ph
P
Ph
R
R = Ph, 93% ee
R = OR', up to 75% ee
R = H, 82% ee
The F. Mathey's team[25] worked on the bridged phosphorous phosphanes of the 1phosphanorbornadiene family. In this family, Bipnor (bis-phosphanorbornadiene) gave
excellent results for the hydrogenation of dehydroamino acids with rhodium as catalyst
(>98% ee). Recently, an easy accessible analogue of Bipnor known as C2-Bipnor was
reported and showed a wider range of applications than Bipnor[25]. Other types of
structures derived from the phosphanorbornadiene backbone[26] are being developed by
Rhodia. In the same way, the G. Balavoine and J.-C. Daran's team used chiral phospholes
in asymmetric hydrogenation catalyzed by rhodium and iridium complexes[27].
2007, July
3 / 30
Me
Me Me
Me
P
Ph
Me
Me
Ph
Ph
P
P
HO
Me
Ph
P
Me
Ph
NR
Me
Ph
Me
Ph
P
CHO
Ph
Ph
(R,R)-BIPNOR
Me
Me
Ph
Me
P
Ph
OH
Ph
C2-BIPNOR
Asymmetric hydrogenation application fields have been widened by the use of chiral
ruthenium complexes. Asymmetric hydrogenation using chiral complexes of ruthenium
through the dynamic kinetic resolution of α-substituted β-cetoesters was discovered in
1989[28-29]. A general method for the synthesis of chiral ruthenium catalysts was
developed by J.P. Genet, V. Vidal and co-workers[30]. This method is compatible with a
large range of chiral diphosphines such as Dipamp which was synthesized on large scale
by the team of S. Jugé[31], phosphetanes[32], chiral phosphetanoferrocenes[33],
dissymmetric atropisomeric diphosphanes such as MeO-NAPhePHOS[34] and triMeNAPhePHOS[35] or symmetric such as SYNPHOS®[36] and DIFLUORPHOS®[37], the last
two being industrially made by Synkem SAS. These ligands were used in the rhodium
and ruthenium-catalyzed asymmetric hydrogenation of a wide range of functionalized
ketones and alkenes with high level of selectivities. Moreover, the Ru-Synphos catalyst
has been successfully used in the synthesis of some industrially relevant key
intermediates and bioactive molecules[38] through dynamic kinetic resolution[39]. The
synthesis of precursors of the liposidomycins and RA-IV derivative was described via
asymmetric hydrogenation of β-ketoesters[40]. Recently, a new generation of chiral
iridium catalysts was developed in collaboration with a Japanese group[41].
2007, July
4 / 30
X
L
R
X
[Ru] ou [Rh] cat./ L*
R
H2
H
H
L
R=alkyle, aryle
L=CO2R', PO2R',SPh, SOPh, SO2Ph
X=C, N, O
R
P
R
R
L* =
PPh2
PPh2
MeO
PPh2
PPh2
P
R
(S,S)-CnrPHOS
(R)-MeO-NAPhePHOS (R)-tri-Me-NAPhePHOS
O
F
PPh2
PPh2
O
O
O
(R )-SYNPHOS®
O
F
O
F
O
F
O
PPh2
PPh2
(R)-DIFLUORPHOS®
Some modified Binap ligands[42] were reported and 4,4’ and 5,5’-Binap derivatives were
used for catalytic asymmetric hydrogenation of ethyltrifluoroacetoacetate[43]. Helicene
derivatives[44], P-chirogenic β-aminophosphine and amino-phosphane phosphinite ligands
were
synthesized[45].
Cyclic
β-iminophosphine
were
used
for
the
asymmetric
hydrogenation of ketones[46] and aminophosphine-oxazoline for iridium-catalyzed
enantioselective hydrogenation of arylimines[47].
H
H
N
Me
O
P
R1 P
P R2
R3
Ph
NH O
N
N
PPh2
Ph
P. Dixneuf's team has also studied the hydrogenation of carbon-carbon double bonds of
cyclic cyclic carbonates[48] and acyloxazolidinones[49] with Binap and DuPHOS ruthenium
catalysts. This study has been extended to the tetralone enamides hydrogenation[50]. P.
Dixneuf and C. Bruneau used this catalytic system in the enantioselective hydrogenation
of tetrasubstituted double bond of enamides with an enantioselectivity up to 72%[51]. C.
Bruneau and coll. reported that chiral rhodium complexes bearing monophosphites
2007, July
5 / 30
ligands were found to be efficient catalysts for asymmetric hydrogenation of βacylaminoacrylates with ee values up to 94%[52].
A.
Mortreux
and
co-workers[53]
demonstrated
that
aminophosphine-phoshinite
derivatives (AMPP) were very efficient in asymmetric hydrogenation of functionalized
ketones with ee up to 99%. These RhAMPP-catalysts together with Ru-MeO-Biphemp
were used respectively in Rh and Ru-mediated hydrogenation reactions of chloroketone
(up to 96% ee) and enamide (up to 98% ee), which were used as key steps for the
synthesis of SR58611A[54]. F. Agbossou and J. F. Paul performed a density functional
study of hydrogenation of ketones catalysed by neutral rhodium-diphosphane
complexes[55].
O
PR2
N
PR2
O
H PR
N
2
PR2
(S)-(R,R)oxoProNOP
O
QuiNOP
R=Cy, Cp
R=Cy, Cp
(OC)3Cr
N
PR2
O
H PR
N
2
PR2
O
H PR
2
(S)-(R,R)indoProNOP
R=Cp
R=Cp
Today, numerous industrial processes use an enantioselective hydrogenation step in the
creation of asymmetric centers. In this context, the team of J.-P. Genet in
collaboration with Firmenich company, discovered an efficient catalytic system for the
hydrogenation of tetra-substituted bonds. This reaction is used for the large-scale
production of (+)-cis-dihydrojasmonate, under the trade name as Paradisone®[56], which
is one of the components of the perfumes of Christian Dior (Dolce vita) and Ralph
Lauren (Romance).
MeO2C
MeO2C
[Ru] cat / L*
H2
ton 2000 ; tof 200 h-1
O
L* = (R,R)-Me-DuPHOS
JOSIPHOS
2007, July
O
Paradisone
ee=90%
6 / 30
The fundamental field of asymmetric hydrogenation has been recognized in 2001 with
the award of the Chemistry Nobel Price to professors R. Noyori[57] and W. S. Knowles[58]
together with professor K.B. Sharpless for his work on asymmetric oxidation.
3 - Hydrogen transfer
Several French teams worked on asymmetric reductions by hydrogen transfer. In 1990,
inspired by the examples of Rh(I) catalyzed hydrogen transfers, the team of R. Chauvin
replaced the hydrogen by isopropanol in basic medium with a ruthenium(II)-Diop
complex[59]. Significant selectivity was obtained (62% ee) by the team of J.P. Genet and
V. Vidal for the reduction of acetophenone and its derivatives, by using several
ruthenium complexes[60]. In 1993, M. Lemaire and co-workers[61] showed that
nitrogenous ligands like diamines could be an interesting alternative to diphosphanes.
They have used amides, ureas and thioures in asymmetric catalysis by hydrogen
transfer reaction catalyzed by rhodium and ruthenium complexes with excellent
selectivities[62]. Theoretical studies on the diamine-rhodium complex structure were
also conducted[63]. Asymmetric hydrogen transfer reductions of prochiral ketones
catalyzed by ruthenium or iridium complexes with chiral bis(oxazolines)[64] and
enantiopure β−aminoalcohols have been reported[65]. Chiral polyaminoalcohols and
polyamino thiols were shown to be effective in the Ru-promoted asymmetric hydrogen
transfer reduction of acetophenone[66].
L* =
O
R'
R
[Ru]/ [Rh] cat./ L*
i-PrOH, base
Ph
Ph
H
H
R1 N C N
N C N R1
OH
X
X
* R'
X=O, S
R
RCH2NH
OBn
OBn
HO
R=Aryle
F. Mathey et al. used a Bipnor ruthenium complex in the hydrogenation of
acetophenone[25]. The team of A. Mortreux described the reduction of β-ketoesters and
other ketones by chiral diamines[67] or ephedrine[68] Ru-complexes and a variety of βaminoalcools has been used for the reduction of aromatic ketones[69]. The team of R.
2007, July
7 / 30
Chauvin tested a rhodium-methyldiopium complex for hydrogen transfer reactions[70]. C.
Mioskowski and his collaborators have described the dynamic kinetic resolution of αamino-β-ketoesters
in
a
formic
acid
/triethylamine
mixture
with
a
chiral
perfluorosulfonated diamine and obtained good enantio- and diastereoselectivities[71].
The team of J. Cossy studied the reduction of symmetric and dissymmetric diketones1,3[72],
and
C-2
substituted[73]
allowing
syn
diastereoisomers
with
good
enantioselectivities.
4 - Asymmetric hydrosilylation and hydroamination
In the early 70's, the team of H.B. Kagan developed the first examples of imines
hydrosilylation catalyzed by Diop-rhodium complex[12]. In 1989, G. Balavoine and his
colleagues described the first use of chiral oxazolines as ligand for asymmetric
hydrosilylation[74]. Recently, the team of R. Chauvin used chiral phosphonium ylures
which catalytic potential had not been explored. In particular not stabilized binapium
ylures ligand[75] and chiral sulfinylphosphoniophosphides ylures[76] led to very fast
rhodium(I) complexes with good activity. J. F. Carpentier and A. Mortreux reported
zinc–diamine-catalyzed asymmetric hydrosilylation of ketones with ee up to 99%[77].
P
P
p-Tol ••
SO
Ph2P C
H
PPh2
Rh
CH2
Y
P = PPh2
Ar
Ar
R1
R1
NH HN
R2
R2
R1=H, Me
R2=Ph, 2-MeO-C6H4, pCl-C6H4, Cyclohexyl...
Ar=C6H4
J. Collin, E. Schultz and co-workers achieved an enantioselective intramolecular
hydroamination catalyzed by lanthanide ate complexes coordinate with N-substituted
(R)-1,1’-Binaphtyl-2,2’ diamido ligands[78] with ee up to 78%.
2007, July
8 / 30
NH
[cat*]
NH2
*
up to 78%
R
N
N
R
N
Ln
N
R R
[Li(thf)4]
Ln=Sm, Nd, Lu, Yb
R=CH2tBu, CH2iPr, CH2Ph, iPr, c-C6H11
5 - PN and PO ligands in homogenous catalysis
In the beginning of the 80's, the teams of A. Mortreux and F. Petit, in collaboration
with the teams of G. Buono et G. Peiffer, developed a new generation of PN, PO and
AMPP (Aminophosphanes Phosphinites) chiral ligands, very useful for the formation of
C-C and C-H[79]. For instance, these ligands proved to be efficient in the hydrovinylation
of cyclohexa-1,3-diene catalyzed by Ni ; the ThreoNOOP ligand gives 93% ee on
vinylcyclohex-3-ene due to its tridentate capacity[80].
OPPh2
[Ni] cat.
*
+
L* =
L*, –30°C
ee = 93%
H
N Me
Ph2PO Me PPh2
ThreoNOOP
The team of A. Mortreux and F. Petit developed further the use of these ligands for CC bonds forming reactions[81]. Thus, AMPP were used for asymmetric hydroformylation
with the first identification of a rhodium hydride complex[82]. A. Mortreux studied the
applications of AMPP ligands in hydrosilylation, hydroformylation, ethylene-diene
hydrovinylation, conjugated diolefin dimerization and allylic nucleophilic substitution[83].
The team of G. Buono developed new chiral monophosphanes, in which the phosphorous
atom is chiral, such as oxazaphospholidines[84] or o-hydroxyarylphosphide derivative[85]
for enantioselective reductions of ketones. A. Alexakis, L. Micouin and co-workers
demonstrated that monodentate ligands such as phosphoramidites and phosphites could
be used for the enantioselective iridium-catalyzed hydroboration of meso-bicyclic
hydrazines[86].
2007, July
9 / 30
OH
O
Cl
Cl BH 3, L* cat.
L* =
e.e. = 94%
O N
P
Ph
O
Another ligand developed by this team, the PN type Quiphos, proved to be efficient in
enantioselective catalysis[87] so were chiral iminodiazaphospholidines with basic
properties, efficient in Cu-catalyzed asymmetric cyclopropanations[88].
N
PhN
N
H
P
Me2N
N
Ph
N
P
N
Ph
Quiphos
6 - Ferrocenyle type chiral ligands
In the field of ferrocenyle chiral ligand chemistry, the team of H.B. Kagan also
developed new ways for asymmetric synthesis avoiding resolution methods[89]. Thus,
several planar chiral ferrocenes were prepared by diastereoselective deprotonation of
chiral sulfoxides[90] or chiral acetals[91]. It was then possible to efficiently get 1,2bis(phosphane)[92], 1,3-bis(phosphane)[93] and 1,1’-bis(phosphetano)ferrocenes[33] that
were very efficient ligand for the asymmetric hydrogenation of dehydroamino acids and
allylic substitution.
R
PPh2
Fe
PR2
PR2
Fe
PPh2
P
R
Fe
R
P
R
7 - Palladium, Iridium, Copper and Ruthenium in metal-catalyzed allylation and
etherification
The asymmetric allylation of stabilized carbanions, catalyzed by chiral palladium
complexes is a very efficient way to obtain C-C bonds. The team of H. B. Kagan and J.-C.
Fiaud described the first asymmetric induction in the late 70's[94]. Thus, β-diketones
and β-ketoesters allylation with the Diop ligand open the way for palladium η3-allyle
complexes in chemistry.
2007, July
10 / 30
O
O
OPh
+
O
[Pd] cat.
(R,R)-DIOP
O
+ PhOH
ta
ee = 15%
This research has been extended by the team of J.-C. Fiaud, setting up the first
enantioselective reaction allowing the creation of axial chiral compounds[95]. The
reaction of malonates on 1-vinylcyclohexanol 4-substituted carboxylates led to an
excellent enantioselectivity by using palladium complexes and the Binap ligand. The
allylic substitution of esters of 1-arylethanol type compounds was also asymmetrically
set up for the first time with (R,R)-Me-DuPHOS[96]. The enantioselectivities of this Pdcatalyzed benzylic reaction were recently improved and reached 90% by using an
isopropyl analogue of DuPHOS ligand[97].
[Pd] cat.
(R)-BINAP
t-Bu
H
OCOR
CH(CO 2Me)2
t-Bu
H
NaCH(CO2Me)2
ee = 90%
The team of J.-P. Genet also worked on stereoselective reactions catalyzed by palladium
complexes. The first glycine derivative imines' allylation was perfomed with the Diop
ligand leading to 68% enantiomeric excess[98].
Ph
N
Ph
MeO2C
[Pd] cat.
(R,R)-DIOP
Ph
CH2=CH-CH2OAc
N
Ph
MeO2C
H
ee = 68%
Inter
and
nucleophiles,
intramolecular
was
cyclopropanes[100]
applied
and
substitution
to
the
β-lactams[101].
reaction
synthesis
The
by
of
synthesis
functionalized
alkaloids[99],
of
carbonated
optically
(-)-chanoclavine
active
I
was
accomplished via this technology in the presence of Pd/Binap system in 60% yield and
95% enantiomeric excess[99].
2007, July
11 / 30
CH2OH
OAc
[Pd] cat
(S)-BINAP
NO2
NO2
NHMe
K2CO3, THF
rt, 60%
HN
HN
ee = 95%
HN
(-)-chanoclavine I
The alkylation of prochiral aryl cyano esters has also recently been investigated by F.
Agbossou-Niedercorn’s group[102]. The use of the chiral pocket ligands of Trost’s group
allowed the formation of quaternary stereogenic centers in ee up to 63%.
Nitrogenated and oxygenated nucleophiles have also been used in this type of reaction
to prepare key intermediates of natural or pharmacologically active products. The
teams of J. Muzart[103] and D. Sinou[104] have thus described the efficient access to the
backbone of vinylic heterocycles or chiral alkylidenes. The cyclization of benzene-1,2diol with various racemic propargylic carbonates in the presence of Binap ligand
afforded
the
corresponding
2-benzylidene-3-methyl-2,3-dihydro-1,4-benzodioxine
derivatives in ee ranging from 40 to 97%[105].
The catalytic properties of the newly synthesized ligands such as the bis(oxazolines) or
the phospholes of the G. Balavoine's team[106] has been evaluated in allylic alkylations. D.
Sinou and his collaborators have recently shown that the use of surfactants associated
with the Binap ligand allowed to carry out this reaction in water[107].
There is still a strong need of novel and original chiral ligands. Recently several French
teams (F. Agbossou-Niedercorn’s, A. Alexakis’, N. Avarvari’s, E. Framery’s, J. Muzart’s,
D. Sinou’s teams) have worked on this area and prepared new chiral ligands that were
tested in standard reactions and more specifically in the Pd-catalyzed asymmetric
allylic alkylation[108].
B. Chaudret’s group recently demonstrated that the Pd-catalyzed allylic alkylation
reaction may also operate differently depending on the nature of the catalyst[109]. Novel
palladium nanoparticles stabilized by chiral diphosphite showed spectacular activity and
were selective to one enantiomer of the substrate (rac- 3-acetoxy-1,3-diphenyl-1propene), hence demonstrating a very high degree of kinetic resolution. This constitutes
the first report of an asymmetric C-C coupling reaction catalyzed by nanoparticles with
2007, July
12 / 30
a high enantiomeric excess and, moreover, the first nanoparticle-catalyzed reaction
outside
hydrogenation
with
the
Pt/cinchonidine
system
leading
to
high
enantioselectivity.
Allylic substitution reactions have still attracted much attention as the control of the
regio- and enantioselectivities are crucial in catalysis. Other metals such as iridium,
copper and ruthenium have been identified as excellent catalysts for allylic
substitution. The group of A. Alexakis has developed highly efficient systems implying
the use of chiral phosphoramidite ligands. In the case of iridium catalyst, the addition
of malonate type or amine as nucleophiles afforded the corresponding branched
derivatives in good to excellent enantioselectivities
[110]
. The use of copper is also highly
challenging as it allows the addition of hard non-stabilized nucleophiles such as small
alkyl or vinyl magnesium derivatives[111].
Et
CH(CO2Me)2
R
For Ir and Cu catalysts
OMe
R'
ee up to 98%
ee up to 98%
[Ir] cat, L*
NaCH(CO2Me)2
X = OCO2Me
L* =
R
O
P N
O
[Cu] cat, L*
EtMgBr
R'
R
X
X = Cl
[Ru] cat, L*
ArOH
X = Cl
OMe
For Ru catalyst
O
Ph
O
N
OAr
Ph
R
Ph
N
Ph
ee up to 82%
The ruthenium-catalyzed allylic etherification reaction was described by the team of C.
Bruneau and J.-L. Renaud. Regio- and enantioselective substitutions of cinnamyl chloride
by various phenols have been achieved in the presence of a Ru/bisoxazoline ligand[112].
8 - Michael type additions
In the field of C-C bond creation with simultaneous control of asymmetric centers,
several French groups developed innovative methodologies and original chiral ligands.
The addition of organometallic derivatives on Michael's acceptors is a fundamental
2007, July
13 / 30
reaction in organic synthesis allowing the creation of C-C bond in ß position of an
activated unsaturated substrate. The team of A. Alexakis and J.-F. Normant was the
first to describe the enantioselective conjugated addition of organocuprates on enones
in the presence of a stoechiometric chiral ligand[113]. This new concept has been quickly
developed in catalysis with the conjugated addition of organozinc compound in the
presence of chiral copper catalysts, leading to enantiometric excess higher than 99% on
various substrates[114]. Trimethyl aluminium has also been employed in copper-catalyzed
Michael addition to various nitroalkenes ee up to 93% using a chiral phosphoramidite.
The synthesis of (+)-ibuprofen was achieved with 82% ee[115].
R'
Et2Zn + R
1
Et
GEA CuX cat.
R1 *
L* cat.
GEA =
Ph
GEA
R
O
L* =
P N
O
COR2,
R
Ph
NO2
R'
A. Alexakis et al. have also recently described an interesting copper-catalyzed
conjugate addition-cyclization in the presence of chiral phosphoramidite cyclic products
were obtained with high diastereoselectivity and 94% ee[116]
O
O
Ph
O
CuX/L*
OMe
Et2Zn/Et2O
-30°C r.t.
CO2Me
Ph
Et
e.e. up to 92%
A. Alexakis in collaboration of S. Gladiali's research group have reported the use of P,
O-bidendate arylphosphine ligand for the asymmetric copper-catalyzed conjugate
addition of dialkylzinc and trialkyl aluminium with the enantiomeric excess reaching 91%.
A synthesis of enriched (R)-muscone (77% ee) was achieved using this procedure[117].
O
O
2 mol. % Cu(CH3Cn)4PF6
L*
H
Me
L* =
PPh2
P(O)Ph2
Et2O
1.5 Me3Al
2007, July
14 / 30
A. Alexakis and the group of S. Roland in Paris have established that stable chiral Nheterocyclic carbenes (NHC) are particularly efficient in copper conjugate addition to a
variety of Michael acceptor. Enantioselectivities reaching 93% were obtained[118].
O
O
L*, Cu(OAc)2
L* = 1-naphthyl
Et2Zn (1.5 eq.)
Et2O, -78°C, 16 h.,
N
Me
1-naphthyl
N
AgCl Me
e.e. = 93%
This approach, employing monodentate ligands is now widely used among people working
on copper based asymmetric synthesis[119]. The asymmetric addition to α-halo enones
was also recently described in excellent yields and selectivites[120]. Enantiomerically
enriched 2-substituted 1,2-dihydroquinolines were obtained by A. Alexakis and coworkers using enantioselective addition of organolithium reagents to quinoline. 1,2diamines or sparteine were used as external ligands and enantiomeric excesses up to
79% were obtained[121].
Asymmetric conjugate addition to β-disubstituted enones has received increasing
interest during the last five years. However, one of the main drawbacks is the lack of
reactivity of β-trisubstituted enones. A. Alexakis and co-workers have designed two
efficient systems for the construction of carbon quaternary chiral centers using copper
chiral diamino carbene ligands with Grignard reagent and alkylaluminium in the presence
of phosphoramidites[122].
O
O
PF6
OH H
1.2 R-MgBr, Et2O
+
Me 3% CuOTf2, 4% ImH
0° or -30°C, 30 min.
R
R
N
N
Me
96% e.e.
R = Butyl
A. Alexakis and co-workers have developed a new method of kinetic resolution of 1,3cyclohexadiene monoepoxide with Grignard reagents leading to good yields, excellent
regioselectivity through SN2 pathway and enantioselectivity up to 90% ee[123].
2007, July
15 / 30
The 1,4-addition of organometallic reagents to unsaturated compounds is one of the
most versatile reactions in organic synthesis. In that context, it has been shown that
trivalent organoboronic acids can efficiently add to unsaturated substrates in the
presence of catalytic amount of rhodium catalysts and have proved to be a very good
alternative to copper catalysts. J.-P. Genet, V. Michelet and co-workers have shown
that the atropoisomeric ligand Digm-Binap[147] in ethylene glycol gave Michael adducts
with excellent enantioselectivities up to 98%. This reaction proceeded with high turn
over number (TON 13200)[124].
O
O
L* =
[Rh] cat.
L* cat., ethylene glycol
RB(OH)2
(CH2)n
H2N
(CH2)n R
NH2Cl
(R)-Digm-Binap
N
H
n = 1, 2
R = Aryl
2
PPh2
90-98% ee
The trivalent organoboron reagents have low toxicity, however many organoboranes are
not highly stable. In contrast, potassium organotrifluoroborates have shown exceptional
stabilities. J.-P. Genet and S. Darses have reported an efficient in situ preparation of
aryl, alkynyl, alkenyl potassium trifluoroborates[125]. An asymmetric version of this 1,4addition of potassium organotrifluoroborates to enones have been described by S.
Darses and J.-P. Genet[126]. Optimization of the conditions revealed that high yields and
enantiomeric excesses could be achieved using cationic Rh(cod)2PF6 complexed with
atropoisomeric Binap, (R,S)-Josiphos and (R)-MeO-Biphep ligands in a toluene/water
mixture as solvent.
O
O
+ R BF3K
Cond a) or b)
R = aryl, alken-1-yl
PCy2
L* =
[Rh] L* cat.
PPh2
PPh2
R
e.e. up to 98%
(R)-BINAP
Fe PPh2
(R,S)-Josiphos
MeO
MeO
PPh2
PPh2
(R)-MeO-Biphep
Compared to Miyaura-Hayashi conditions using organoboronic acids derivatives this
reaction using organopotassium trifluoroborates generally required lower amounts of
the organometallic reagent. Using potassium vinyltrifluoroborate, high yields of
vinylated Michael adducts were obtained.
2007, July
16 / 30
These conditions proved to be general for the functionnalization of other Michael
acceptors like α,β-unsaturated amides[127] and esters[128].
R1
EWG +
R2
BF3K
R2
Rh(cod)2PF6 3 mol%
R1
(R)-binap
tol/H2O, 110°C
EWG
yld: > 70%
ee: 87-99%
R1 = alkyl
R2 = aryl, alken-1-yl
EWG = keto, ester, amide
9 - Enolates in enantioselective catalysis
The enolate enantioselective protonation allows a good control of the asymmetric
center α of a carbonyl function. The French team of J.-C. Plaquevent and L. Duhamel
first introduced this concept[129].
The team of J. Muzart showed that in the presence of a catalytic amount of palladium,
it was possible to generate in situ an enolic specie from several substrates, which is
protonated in an asymmetric and catalytic way by using an aminoalcohol[130].
O
R2
R1
O
A*H cat.
R1
R2
The
use
of
ketoesters
deprotection/decarboxylation/
2
* R
R2
and
enol
ethers
enantioselective
led
protonation
to
ketones
sequence,
via
when
a
the
hydrogenation of α,β-unsaturated ketones implies 1,4 addition of hydrogen. Previously,
this team became famous for the dienols asymmetric protonation produced by Norrish
II type photorearrangement of carbonylated α,β-unsaturated compounds[131].
J.-P. Genet, S. Darses and co-workers have developed recently a new reaction of 1,4addition/tandem enantioselective protonation allowing a direct access to amino acids[132].
Thus, the Michael type addition of organometallics on dehydroamino esters with chiral
rhodium catalyst, generates catalytic species of rhodium enolates that are protonated
by 2-methoxyphenol (guaiacol), an achiral proton source. Indeed the conjugate addition
of potassium aryl and alkenyl-trifluoroborates to N-acylamidoacrylate furnishes a
variety of α-amino acid derivatives with good enantioselectivities. Under these
conditions, boronic acids gave low conversion and modest enantiomeric excesses (40%).
2007, July
17 / 30
NHAc
+
CO2Me
R
[Rh(cod)2][PF6] 3 mol%
R BF3K
(R)-Binap 6.6 mol%
Guaiacol, Tol, 110°C
CO2Me
68–96 % yield
81–90% ee
R = aryl, alkenyl
10 -
NHAc
Enantioselective deprotonations
Asymmetric reactions under the influence of a chiral base, were the object of intense
research in the last decades. The French team of J.-C. Plaquevent and L. Duhamel for
the amino acid deracemization did the first description of the use of a stoechiometric
chiral base[133]. The same team also developed the first enantioselective catalytic
deprotonation by using a chiral base[134].
H
O
O
Br
H
Br
Br
B-K+ cat.
H
KH, MeOH,–80°C
O
O
B- =
-O
Ph
NMe2
ee > 98%
11 -
Asymmetric oxidation reactions
Among the numerous oxidation reactions, the French chemists’ works are mainly
distinguished in the field of sulfide asymmetric oxidation into sulfoxides and the
enantioselective allylic oxidation. In 1984, the team of H.B. Kagan set up for the first
time a system derived from the Sharpless reagent by water addition allowing the
asymmetric oxidation of sulfides into chiral sulfoxides, with ee over 90%[135]. This
method developed between 1984 and 1996, has been modified by the firm Astra-Zeneca
to produce Esomeprazole, used for the treatment of ulcers. The metallocenes
sulfoxides have appeared as excellent ligands for asymmetric catalysis[136].
The team of M. Fontecave[137] get also interest to the sulfide oxidation into sulfoxide
with iron and ruthenium complexes.
S
Ar
TBHP ou CHP
O
:
R
[Ti] cat.
(R,R)-DET / H2O
R
S
Ar
The teams of J. Muzart and D. Sinou worked on cupro-catalyzed allylic oxidation of
several cycloalkenes. The unsaturated ester are obtained by using enantiopure amino
2007, July
18 / 30
acids as chiral ligands[138] or fluorated bis(oxazolines)[109]. Oxidation reaction of non
functional olefin are also of main interest. The groups of D. Mansuy[140], B. Meunier[141]
and E. Rose[142] have developed ingenious oxidation methods using metallic catalysts
derived from salens and porphirins. The asymmetric epoxidation of alkenes was recently
reported by the group of Muzart in the presence of a ruthenium[143] or manganese[144]
catalysts containing sugar based ligands.
12 -
Recycling in asymmetric catalysis
One of the challenge of asymmetric catalysis is the development of new processes
allowing easier separation and recycling of the catalyst. A seducing solution for
industrial processes is the use of two-phase systems, either liquid / liquid or liquid /
solid where the catalyst and the product remain in different phases. One of the
approach to make these two-phase systems is to prepare ligands with a strong affinity
for one of the phase. The pioneer work of H.B. Kagan on the Diop ligand immobilization
on polymer[14], have undoubtedly inspired the later research in this field. Some
contributions were developed in France by the teams of J.-P. Genet, M. Lemaire, D.
Sinou and J. Collin in the field of perfluorinated or hydrosoluble ligands for liquid/ liquid
systems, and also for liquid / solid systems with the preparation of supported ligands.
Several families of ligands known for their efficiency in homogeneous C-H, C-C and C-O
bonds
formations,
have
been
functionalized
by
hydrosoluble,
perfluorinated,
polyethylene glycol groups or incorporated in matrices to form new materials.
Hydrosoluble
sulfonated
phosphanes
derived
from
chiral
ligands
such
as
Cyclobutanediop, Skewphos, and Chiraphos, associated with rhodium or palladium,
allowed the reduction of amino acids and imines precursors and the hydrocarboxylation
of styrene derivatives, in two-phase systems[145].
In the atropoisomeric ligands family, Binap and Mop have been modified (ammonia,
guanidinium, perfluorinated group).
2007, July
19 / 30
PAr2
PAr2
Ar2P
PAr2
Ar2P
PAr2
Ar = -C6H4-m-SO3Na
R
C8F17
R
PPh2
PPh2
PPh2
PPh2
R'
PPh2
OCH2C7F15
C8F17
R
R = R' = NH2, (R)-Diam-BINAP
R = R' = NHC(=NH2)NH2Cl, (R)-Digm-BINAP
R = CH2NH3Br
R = NHCO(CH2)3CO(OCH2)nCH2OMe,
R = C6F13, C8F17
R' = NH2, PEG-(R)-Am-BINAP
R = R' = NHCO(CH2)3CO(OCH2)nCH2OMe
C8F17
C8F17
C8F17
O
NH
O
N
NH
C8F17
silice
C8F17
N
R
O
O
Si
EtO
3
NH
O
O
O
Si OEt
3
HN
O
O
N
N
O
R
R = Ph, i-Pr
O
O
C8F17
These derivatives proved to be efficient for the asymmetric hydrogenation of alkenyl
or carbonyl derivatives[146-148], allylic substitution[149], or allylic oxidation[145] whether in
water, in perfluorinated media, ionic liquids or supercritical CO2 media. Chiral diamines
(and diimines) functionalized by perfluorinated groups have also given good to excellent
results in asymmetric hydrogenation by hydride transfer[150] and promising enantiomeric
excesses in allylic substitution and cyclopropanation reaction[151]. Oxazolines were also
efficient
for
Diels-Alder
reactions[152],
asymmetric
allylic
oxidation[103-107]
and
cyclopropanation reaction[153]. All these systems often led to the same efficiency and
enantioselectivity that the ones obtained with a parent-ligand, but they have the
benefit of being recyclable.
An original concept for recycling asymmetric bis(oxazoline)-type catalysts was reported
by Schulz’ group[154]. The formation of a charge-transfer complex between the chiral
ligand and trinitrofluorenone that could be precipitated allowed the authors to recycle
the catalyst several times in asymmetric Diels-Alder reactions.
2007, July
20 / 30
13 -
Asymmetric C-C, C-O and C-N bond creation
The formation of carbo- and heterocycles is also a very promising research field to
produce highly functionalized intermediates. The team of G. Balme[155] has recently
described the asymmetric version of the first cyclization of unsaturated derivatives
with a Wacker type reaction . The group of D. Sinou has shown that the asymmetric
arylation of 2,3-dihydrofuran with aryl triflates could be conducted in water in the
presence of Binap and surfactants and afforded the thermodynamic alkene in ee up to
67%[156].
The formation of C-C bonds has also been well reported by the team of H. B. Kagan,
using phase transfer conditions[157]. Functionalized Schiff bases' enantioselective
alkylation, catalyzed by nickel complexes led to mono and disubstituted α-amino acids.
Other types of polyethylene glycol supported systems also led to the synthesis of αamino acids through glycine alkylation[158]. Other French contributions to C-C bond
forming
reactions
concern
polymerization
using
palladium
complexes
and
bisoxazolines[159], the cyclopropanation of styrene derivatives with bipyridine or
terpyridine type of ligands[160], the allylation of aldehydes in the presence of an
heterogeneous chromium catalyst[161] or the methoxycarbnylation of alkene[162]. The
first example of a total axial chirality transfer was reported by the group of M.
Malacria in the [2+2+2] cycloaddition of allendiynes[163]. H. B. Kagan and Y. N. Belokon
reported the asymmetric addition of TMSCN to benzaldehyde catalyzed by salens. They
showed that a mixture of two salen derived VV and TiIV complexes resulted in the
formation of a mixed complex which exhibited catalytic properties derived from both
organometallic species[164].
The group of J.-P. Genet and V. Michelet have conducted for the first time an
asymmetric cycloisomerization of 1,6-enyne, leading to a tandem formation of C-C and
C-O bonds. Enantiomerically enriched functionalized carbo- and heterocycles were
obtained in the presence platinum and a chiral monodentate atropisomeric ligand with ee
up to 85%[165]. The group of G. Buono described the first cobalt-catalyzed cycloaddition
of cycloheptatriene with alkynes and therefore synthesized functionalized bicyclic
derivatives in good yield and ee up to 74%[166]. The formation of C-N bonds was achieved
2007, July
21 / 30
via Sm-catalyzed reactions[167]. The aza-Michael reactions of α,β-unsaturated-Nacyloxazolidinone afforded the aspartic acid derivatives in ee up to 88%. The same
catalyst was also efficient for the enantioselective ring opening of meso-epoxides by
aromatic amines leading to amino alcohol derivatives in good yield and ee up to 93%.
14 -
Asymmetric amplification and multi-substrate screening
H. B. Kagan and co-workers demonstrated asymmetric amplification in the addition of
diethylzinc on aromatic aldehydes[168] and by kinetic resolution using a racemic reagent
in amine acetylation[168]. The same group presented the principle of one-pot multi
substrate screening which was successfully applied to several types of catalyzed
enantioselective reactions[169].
15 -
Conclusion
Asymmetric catalysis is a great tool for organic synthesis. Some of the systems
compete with and sometimes match biological systems. It is more and more used
worldwide for the production of chiral intermediates. This presentation, which doesn't
pretend to be complete, shows the intense activity of the French laboratories working
in collaboration with the industrial world. This catalysis field contributes efficiently to
the concept of green chemistry and sustainable development.
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Asymmetric Organometallic Catalysis

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