A β-Carbon elimination strategy for convenient: In situ access to cyclopentadienyl metal complexes

Article abstract of DOI:10.1039/c7sc02986a

The electronic and steric properties of tailored cyclopentadienyl (Cp) ligands are powerful handles to modulate the catalytic properties of their metal complexes. This requires the individual preparation, purification and storage of each ligand/metal combination. Alternative, ideally in situ, complexation protocols would be of high utility. We disclose a new approach to access Cp metal complexes. Common metal precursors rapidly react with cyclopentadienyl carbinols via β-carbon eliminations to directly give the Cp-metal complexes. An advantage of this is the direct and flexible use of storable pre-ligands. No auxiliary base is required and the Cp complexes can be prepared in situ in the reaction vessel for subsequent catalytic transformations.

Full text of DOI:10.1039/c7sc02986a

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β-Carbon Elimination Strategy as Convenient in situ Access to
Cyclopentadienyl Metal Complexes
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
b
b
a
G. Smits, B. Audic, M. D. Wodrich, C. Corminboeuf,* and N. Cramer*
DOI: 10.1039/x0xx00000x
The electronic and steric properties of tailored Cyclopentadienyl (Cp) ligands are a powerful handle to modulate their
catalytic properties of their metal complexes. This requires the individual preparation, purification and storage of each
ligand / metal combination. Alternative, ideally in situ complexation protocols would be of high utility. We disclose a new
approach to access Cp metal complexes. Common metal precursors rapidly react with cyclopentadienyl carbinols via β-
carbon eliminations giving directly the Cp-metal complexes. Advantages are the direct and flexible use of storable pre-
ligands. No auxiliary base is required and the Cp complexes can be prepared in situ in the reaction vessel for subsequent
catalytic transformations.
www.rsc.org/
should be as well useable with a range of different transition-
metals.
Introduction
Cyclopentadienyl (Cp)–coordinated transition-metal complexes
Organometallics by
β
-Carbon Elimination
are ubiquitous and many of them are efficient catalysts for a
1
OH
[M]
O
O
broad range of versatile atom-economic transformations
.
[M] OH +
R
R [M] +
Many of these reactions have highly optimized conditions, but
use commercially available complexes with a conserved Cp* or
Cp ligand. Only recently, the modulation of the electronic and
steric properties of tailored Cp ligands was recognized as a
R
ꢀ
H O
2
Csp-[M]
OH
Csp2-[M]
Csp3-[M]
OH
η3-allyl-[M]
OH
η5-Cp-[M]
HO
OH
2
powerful tool to overcome sluggish reactivity, to address
3
regio- and positional issues, as well as entry to
this work
4
enantioselective processes. In rapid reaction discovery and
[M]
O
[M]
optimization, the ability to combine a library of ligands with a
library of metal complexes, performing an in situ complexation
to give the desired catalyst species is a relevant advantage.
While this approach is very common for reactions involving for
instance phosphine ligands, it is yet elusive for Cp ligands. In
this case, each ligand / metal combination has to be
synthesized individually, purified and stocked prior to any use
in catalysis. The typical complexation of common Cp* and Cp
[M]
[
M]
[
M]
transient species in catalysis
rearrangements allylation
preparative tool
alkynylation
arylation
product
Scheme 1. Generation of organometallics by βꢀcarbon elimination strategy.
5
complexes involve the metal as limiting reagent. However,
x
highly elaborated Cp or chiral Cp ligands require the use of the
β-Carbon eliminations have been reported as complementary
7
method to access organometallic species in catalysis.
CpH derivative as strictly limiting reactant. In particular for
x
chiral Cp ligands, one has to rely on undesirable reaction
Normally the forward reaction - the addition across a carbonyl
group - is favored and reversing this pathway requires some
additional driving force. This could be a combination of the
right transition-metal and the use of substrates leading to the
conditions, for example involving thallium alkoxide in
4
d,6
benzene.
These shortcomings make the development of
complementary complexation strategies a priority. Ideally,
such technology proceeds rapidly and in quantitative manner,
without the generation of inhibiting reaction byproducts. It
8
9
formation of a stronger Csp-[M] or Csp2-[M] bonds. The
generation of Csp3-[M] requires energy-rich starting materials
10
such as tert-cyclobutanols releasing strain upon β-C
1
elimination. Particular classes are homoallylic alcohols that
1
1
2
can give π-bound allyl-metal species by retro-allylation.
Along the same lines, a cyclopentadienyl carbinol would give
upon C-C bond cleavage a Cp-[M] species. The very strong
bond of the cyclopentadienyl anion to the transitions-metal
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would be a very strong driving force. So far, the β-C
elimination methodology has been used exclusively as an
elementary step in catalytic transformations. Herein we exploit
its potential for the preparation to access Cp-metal complexes.
2
3
4
5
6
7
8
9
2b
2c
2d
2e
2f
H
Ph
Cs
Cs
Cs
Cs
Cs
Cs
-
2
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
1 h
95
10
99
93
30
20
75
75
45
<5
<5
89
80
95
H
CO
2
Et
2
3 h
Me
Me
2
3 h
CH
CH
CH
2
(CH
CH
OCH
2
)
3
CH
2
2
3 h
Results and discussion
2
2
2
CH
2
2
1 h
The required cyclopentadienyl carbinols substrates for the pre-
ligands are accessed in straight forward manner by deprotonation
and addition across the desired aldehyde or ketone (Scheme 2, see
2g
2h
2i
2
2
3 h
1
3
CO
CO
CO
CO
CO
2
Me
2
Me
2
Me
2
Me
2
Et
Ph
15 min
3 h
SI for details). In contrast to many lightly substituted
cyclopentadienes which frequently undergo Diels-Alder
dimerization, all prepared Cp-carbinols are stable and do not
dimerize upon storage. Exemplarily for [Rh(cod)OH]
, ligand, 10
Me
tBu
Cs
-
2
CO
3
2j
1 h
2
exchange of the hydroxy ligand by 2 would break up the dimer and
release a molecule of water to give intermediate 3. In turn, 3 is
predisposed for the final β-C elimination step to yield the Cp metal
complex 4a and ketone 1.
1
1
1
1
1
1
2
3
4
5
2k
2l
CF
3
Cs
Cs
-
2
CO
3
3
1 h
CO
Ph
Cy
Ph
2
Et
2
CO
3 h
2m
2n
2o
Me
Me
15 min
3 h
Cs
-
2
CO
3
CF
3
1 h
a
Conditions: N
.040 mmol additive, 0.2
Yield determined by NMR with an internal standard.
2
atmosphere, 0.040 mmol 2, 0.024 mmol [Rh(cod)OH] ,
2
b
0
M in toluene at 70 °C for the indicated time.
Among the tested substrates, the dimethyl-type carbinol
moiety was further investigated albeit its lower reactivity as it
releases only volatile acetone as by-product (Table 2). It
Scheme 2. a) Synthesis of Cp pre-ligand carbinols 2. b) Envisioned β-C
elimination to access Cp*Rh(I) complexes.
provides a clean complexation giving a range of complexes
with different bulk, ranging from Me Cp (Entry 1) to tBuMe Cp
Entry 5). While substrates with bulky groups react very
With a selection of carbinols with sterically and electronically smoothly, less substituted one like trimethyl Cp precursor 5b
4
3
4
(
1
2
different substituents R and R were initially evaluated (Table 1). A
variety of factors influenced the reaction performance. An aromatic
react less efficiently due to some fulvene byproduct formation.
Indenyl complexes can be prepared with similar efficiency
1
2
substituent R or R was found to be beneficial for yield and
reactivity. A tertiary hydroxyl group is better than a secondary one.
Strained ketone derived 2f and 2g (Entries 6-7) underwent partially
the alternative strain-release pathway, opening the four-
membered ring instead of leading to the Cp-metal species. Most
substrates required the addition of cesium carbonate for shorter
reaction times. Without rhodium complex, carbinols 2 are stable
and no conversion to free Cp*H was observed. Notably, some
substrates displayed significantly increased reactivity and did not
require the addition of any base (Entries 8, 10, 13, 15). The two
(
Entries 6-7). Methyl phenylglyoxylate and acetophenone
derived pre-ligands 5i and 5j are easier accessible and better
suited in the complexation giving as before fast and clean
transformations without the requirement of basic additive
10
(Entries 8-9). Importantly, this complexation strategy is equally
successful for chiral Cp* ligands equipped with our atropchiral
f-j
backbone. Importantly, the β-C eliminative complexation is
not limited to rhodium. For instance, using [Ir(COD)OH] as
4
2
metal salt provided access to indenyl Ir(COD) and
fastest ones were 2h (Ph/CO
2
Me) and 2m (Ph/Me).
cyclopentadienyl complexes 6g-6j in comparable yields (Entries
x
-9). Exposure of chiral Cp * pre-ligand 5k to the reaction
6
Table 1. Evaluation of the influence of the carbinol substituents on the β-C
a
elimination.
conditions induced a smooth complexation, providing rhodium
complex 4k in 93 % yield (Entry 10). This is particularly
4
d, 4f
noteworthy as classical complexation methods
for di-
x
substituted chiral Cp ligand failed completely for this chiral
penta-substituted analog. In analogy, the chiral iridium
complex 6k could be obtained in 87 % yield. Moreover, we
x
III
1
2
b
could extend the method for the preparation of chiral Cp *Co
Entry
1
2
R
R
Additive
Cs CO
Time
3 h
% Yield
complex 7k (entry 11). For the first time, chiral fully penta-
substituted cyclopentadienyl rhodium, iridium and cobalt
complexes are now accessible. This sets the stage for future
2a
H
nPentyl
2
3
39
2
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c
d
2 3
applications in asymmetric catalysis, especially for an internal standard. 4Å molecular sieves instead of Cs CO at 23°C.
e
f
With [Ir(COD)OH]
2
for 6. Isolated yield. Conditions: 0.06 mmol 5k and 36
transformations where previous reported complexes with the
4
o
μmol Co (CO) , 0.4 mL CH Cl at 40 C, then I (0.06 mmol).
2
8
2
2
2
a, 4b
disubstituted chiral variants
reactivity.
failed to provide adequate
Besides the hydroxyl bridged dimer, other [Rh(cod)X]
complexes (X = OMe, OAc, Cl) can be used (Table 3, Entries 1-
). The chloride containing complexes require addition of KOH
for an in situ exchange. Moreover, [Rh(nbd)X] (nbd =
norbornadiene) and [Rh(CO) Cl] work similarly (Entries 4-6).
Without a change in protocol, the corresponding iridium(I)
complex 6a and cobalt(0) complex were prepared (Entries 7-
). Solely the rhodium ethylene congener is not well suited for
these conditions (Entry 9). However, an improved protocol
vide infra) solved this issue and provided 4n and 4o (Entry 10
2
a
Table 2. Scope for the Cp complexation by β-C elimination.
3
2
2
2
8
8
1
2
b
Entry
1
5
R
R
4
% Yield
(
and 11).
5b
Me
Me
42
a
Table 3. Scope with different transition-metal precursors.
2
3
4
5
5c
5d
5e
5f
Me
Me
Me
Me
Me
Me
Me
Me
80
95
90
95
b
Entry
CpM
4a
4a
4a
4l
[M]
additive
time
3 h
% Yield
1
2
3
4
5
6
7
[Rh(cod)OMe]
2
Cs
Cs
2
CO
3
3
70
d
90 (4g)
8 (6g)
6
5g
5h
Me
Me
Me
Me
8
[Rh(cod)OAc]
[Rh(cod)Cl]
[Rh(nbd)Cl]
[Rh(nbd)OH]
[Rh(CO) Cl]
[Ir(cod)OH]
[Co (CO)
2
2
CO
3 h
70
2
KOH
KOH
3 h
90
2
2 h
80
d
95 (4h)
6 (6h)
7
8
4l
2
Cs
2
CO
3
3
3 h
99
4m
6a
8
2
2
KOH
15 min
5 h
49
2
C
-
S
2
CO
92
c,d
60 (4i)
4(6j)
8
5i
Ph
CO
2
Me
c
4
8
2
8
]
6
h
60
9
4n
4n
4o
[Rh(C
[Rh(C
2
H
4
4
)
2
2
OAc]
2
Cs
2
CO
3
1 h
5 h
1 h
10
70
d
1
0
2
H
)
Cl]
2
KOH, 4 Å MS
KOH, 4 Å MS
c,d
95 (4j)
3 (6j)
e
f
9
5j
Ph
Me
11
[Rh(C
2
H
3
TMS)Cl]
2
66
6
a
2 3
Conditions: 0.04 mmol 2d, 24 μmol [M], 0.04 mmol Cs CO or 0.12 mmocl
b
KOH, 0.2 mL toluene. Determined by NMR with an internal standard.
Conditions: 0.06 mmol 2d and 36 μmol Co
With 2m instead of 2d at 23 °C. With 2m instead of 2d. Isolated yield.
o
d
2
(CO)
8 2 2
, 0.4 mL CH Cl at 40 C.
e
f
e
e
d
0
93 (4k)
For the Ph/Me substrate 2m, DFT computations (at the
1
5k
Ph
2
CO Me
1
PBE0 -dDsC /TZ2P//M06 /def2-SVP level in implicit
4
15
16
8
7 (6k)
1
7
toluene solvent using COSMO-RS, see SI for additional
details) provided some more details on the reaction profile
of the complexation reaction (Figure 1). First, the
[Rh(cod)OH] fragment leads forms complex 3 with the
substrate carbinol. Cleavage of the C-C bond proceeds via
TS1 with a barrier of only 16.3 kcal/mol, which aligns well
with the experimentally observed fast reaction. After C-C
cleavage, a metastable species (Int 1) is formed which quickly
dissociates to the products 4a and 1m after dissociation of
the ketone (TS2). The overall process is thermodynamically
favourable, being exergonic by 34.5 kcal/mol.
f
e
1
1
5k
Ph
2
CO Me
32
a
Conditions: 0.04 mmol 5, 0.024 mmol of [Rh(COD)OH]
2
, 0.040 mmol
b
Cs
2
CO
3
, 0.2 mL toluene at 70 °C, 15 min – 10 h. Determined by NMR with
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Figure 1. Reaction profile of the β-C elimination of carbinol 2m.
While the outlined protocol works very well for robust diene
containing metal precursors, some more sensitive ones, e.g.
2 4 2 2
[Rh(C H ) OAc] resulted in unsatisfactory yields despite full
conversion. DFT computations indicated that the height of
the β-C elimination barrier was not the issue. We
hypothesized that the reaction rate could be negatively
impacted by the increasing amount of formed water. This
could compete with the sterically hindered cyclopentadienyl
carbinol and be the limiting factor in the ligand exchange of
the metal hydroxy complex. Indeed, the addition of 4 Å
molecular sieves as trap for the generated water byproduct
accelerates the reaction significantly (Table 3, entry 10).
Instead of 70 °C, fast and complete complexation occurs at
ambient temperature. Under these conditions, the β-carbon
1
elimination was monitored by H-NMR spectroscopy (Figure
2). From all tested substrates, the initially selected Cp*
dimethyl carbinol 2d was the slowest one. Methyl
phenylglyoxylate derived substrate 2h initially reacts very
fast, but stalls at around 80 % yield. Acetophenone derived
substrate 2m reacts smooth and clean, producing the desired
complex in 90 % yield after 30 minutes and quantitatively
after 1 hour at ambient temperature. Moreover, some
dependence on the substitution pattern of the aryl group
was found. For instance, the p-nitro derivative 2p reacts
fastest and the p-methoxy congener 2q is slower the parent
substrate 2m. DFT results of this substrate set confirmed the
observed reactivity trends. Figure 2b clearly shows that the
substitution pattern strongly influences the TS1 barrier
height, with the slower substrate 2d (21.1 kcal/mol) having
Figure 2. a) Complexation rates of different carbinols
after 60 min: 2d: 22 %; 2h: 82 %; 2m: 99 %; 2p: 99 %; 2q: 75 %. b)
Reaction profile of carbinols in the complexation.
2; Yields of 4a
2
Besides base-free complexation avoiding toxic solvents and
bases, the instant preparation and direct subsequent use in
catalysis of the formed Cp-metal complex is a salient feature
of this protocol (Scheme 3). As example for Rh(III)-catalysis,
the regioselective dihydroisoquinolone formation with
t
terminal 1-decene is shown using the in situ formed Cp Rh(I)
complex 4p. This protocol provides 10 in similar yield and
regioselectivity as previously reported by Rovis with an
t
3a,b
isolated Cp Rh complex. Simple precatalyst 2d could be
used to access 4a, which in turn was used for a synthesis of
isoquinolone 12 with reversed regioselectivity, again with
comparable yield and regioselectivity as previously observed
the highest barrier and the fastest substrate, p-NO bearing
2
2p having the lowest (15.4 kcal/mol).
1
8
by us. Vinyl-TMS bearing complex 4o is hardly accessible by
reduction of [Cp*RhCl ] and simplifies applications in
Cp*Rh(I) catalysis. For instance, it is a competent catalyst for
2
19
intramolecular transfer olefinations of piperidinyl amide 11
4
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x
providing enamide 12. In addition, chiral Cp Ir(I) complex 6k
could be smoothly oxidized with iodine to Ir(III) species 13
should enhance the convenience in applying them in
catalysis and allow exploiting more rapidly the untapped
potential of tailored Cp ligands. In particular, we expect this
as door-opener for further application of chiral Cp* metal
complexes in catalysis.
.
This catalyst provides promising preliminary results for
3
oxime-directed asymmetric C(sp )-H functionalizations of
2
0
substrate 14 yielding tosylamide product 15
.
Acknowledgements
This work is supported by the EPFL and the Swiss National
o
Science Foundation Consolidator Grant n 157741. G. S.
thanks EC 7th Framework Program project REGPOT-CT-2013-
3
16149-InnovaBalt.
Notes and references
1
J. Hartwig, Organotransition Metal Chemistry: From Bonding
to Catalysis; University Science Books: Sausalito, CA, 2010.
a) T. A. Davis, C. Wang and T. Rovis, Synlett, 2015, 26, 1520;
b) T. Piou and T. Rovis, J. Am. Chem. Soc. 2014, 136, 11292;
c) T. Piou and T. Rovis, Nature, 2015, 527, 86; d) F. Romanov-
Michailidis, K. F. Sedillo, J. M. Neely and T. Rovis, J. Am.
Chem. Soc. 2015, 137, 8892; e) Y. Hoshino, Y. Shibata and K.
Tanaka, Adv. Synth. Catal. 2014, 356, 1577; f) T. K. Hyster
and T. Rovis, Chem. Commun., 2011, 47, 11846; g) Y. Shibata
and K. Tanaka, Angew. Chem. Int. Ed. 2011, 50, 10917.
2
3
4
a) T. K. Hyster, D. M. Dalton and T. Rovis, Chem. Sci. 2015,
2
J. M. Neely and T. Rovis, J. Am. Chem. Soc. 2014, 136, 2735;
d) M. D. Wodrich, B. Ye, J. F. Gonthier, C. Corminboeuf and
N. Cramer, Chem. – Eur. J. 2014, 20, 15409.
For a recent review see: a) C. G. Newton, D. Kossler and N.
Cramer, J. Am. Chem. Soc. 2016, 138, 3935; b) B. Ye and N.
Cramer, Acc. Chem. Res. 2015, 48, 1308; for selected
examples, see: c) G. Erker and A. A. H. van der Zeijden,
6,
54; b) T. K. Hyster and T. Rovis, Chem. Sci. 2011, , 1606; c)
2
Angew. Chem., Int. Ed. 1990, 29, 512; d) B. Ye and N. Cramer,
Science, 2012, 338, 504; e) T. K. Hyster, L. Knorr, T. R. Ward
and T. Rovis, Science, 2012, 338, 500; f) B. Ye and N. Cramer,
J. Am. Chem. Soc. 2013, 135, 636; g) D. Kossler and N.
Cramer, J. Am. Chem. Soc. 2015, 137, 12478; h) G. Song, W.
W. N. O and Z, Hou, J. Am. Chem. Soc. 2014, 136, 12209; i)
M. Dieckmann, Y.-S. Jang and N. Cramer, Angew. Chem., Int.
Ed. 2015, 127, 12317.
5
a) R. Dubois (The Dow Chemical), US4962253 A, 1990; b) R.
B. King, Inorg. Chem. 1963, 2, 528; c) M. D. Rausch and R. A.
Genetti, J. Org. Chem. 1970, 35, 3888; d) N. Weding, R.
Jackstell, H. Jiao, A. Spannenberg and M. Hapke, Adv. Synth.
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and D. M. Heinekey, in Inorg. Synth., John Wiley & Sons, Inc.,
2
007, pp. 228; f) H. Chen, J. Hartwig and T. C. Semple, (Shell
Scheme 3. In situ Cp metal complex preparation and direct application in
Rh(III), Rh(I) and Ir(III) catalysis. PMP=4-methoxyphenyl
Internationale Research Maatschappij B.V.; Yale University)
WO 01/64689 A1, 2001.
6
7
a) T. E. Bitterwolf, T. L. Hubler and A. L. Rheingold, J.
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Conclusions
In summary, we have reported a new complexation strategy
to access late transition-metal Cp complexes. A rapid β-
carbon elimination of cyclopentadienyl carbinols in the
presence of a common metal precursor provides access to a
wide range of Cp metal complexes. The advantages of this
process are the direct and flexible use of storable pre-
ligands. No auxiliary base is required and the Cp complexes
can be prepared in situ in the reaction vessel. This protocol
For a review, see: a) D. J. Mack and J. T. Njardarson, ACS
Catalysis, 2013, 3, 272; b) T. Seiser and N. Cramer, Synlett
2
011, 4, 449; c) M. Murakami and T. Matsuda, Chem.
Commun. 2011, 47, 1100; d) K. Ruhland, Eur. J. Org. Chem.
012, 14, 2683; e) M. Miura and T. Satoh, in Palladium in
2
Organic Synthesis (Ed.: J. Tsuji), Springer Berlin Heidelberg,
Berlin, Heidelberg, 2005, pp. 1-20.
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Journal Name
8
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Chemical Science
View Article Online
DOI: 10.1039/C7SC02986A
Stable pre‐ligands and common metal salts provide via β‐carbon elimination access to Cp‐metal
complexes suitable for in situ catalyst preparation.