Linear-selective hydroarylation of unactivated terminal and internal olefins with trifluoromethyl-substituted arenes

Article abstract of DOI:10.1021/ja505579f

We report a series of hydroarylations of unactivated olefins with trifluoromethyl-substituted arenes that occur with high selectivity for the linear product without directing groups on the arene. We also show that hydroarylations occur with internal, acyclic olefins to yield linear alkylarene products. Experimental mechanistic data provide evidence for reversible formation of an alkylnickel -aryl intermediate and rate-determining reductive elimination to form the carbon - carbon bond. Labeling studies show that formation of terminal alkylarenes from internal alkenes occurs by initial establishment of an equilibrating mixture of alkene isomers, followed by addition of the arene to the terminal alkene. Computational (DFT) studies imply that the aryl C - H bond transfers to a coordinated alkene without oxidative addition and support the conclusion from experiment that reductive elimination is rate-determining and forms the anti-Markovnikov product. The reactions are inverse order in α-olefin; thus the catalytic reaction occurs, in part, because isomerization creates a low concentration of the reactant α-olefin.

Full text of DOI:10.1021/ja505579f

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Communication
Linear-Selective Hydroarylation of Unactivated
Terminal and Internal Olefins with Electron-poor Arenes
Joseph S. Bair, York Schramm, Alexey G. Sergeev, Eric Clot, Odile Eisenstein, and John F. Hartwig
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja505579f • Publication Date (Web): 29 Aug 2014
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Linear-Selective Hydroarylation of Unactivated Terminal
and Internal Olefins with Trifluoromethyl-substituted
Arenes
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Joseph S. Bair,‡ York Schramm, ‡ Alexey G. Sergeev,‡ Eric Clot,¶ Odile Eisenstein,¶ and John F. Hart-
wig‡*
‡Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, and
Department of Chemistry, University of California, Berkeley, California 94720, United States.
¶Institut Charles Gerhardt, UMR 5253 CNRS, Université Montpellier 2, cc 1501, Place Eugène Bataillon, 34095 Montpellier,
France.
Supporting Information Placeholder
less than 20%, the selectivity was much higher than that for
any reported3 addition of a simple aryl C-H bond to an alkene
(Scheme 1). Other carbene ligands formed less active catalysts
for this reaction.6
ABSTRACT: We report a series of hydroarylations of unacti-
vated olefins with trifluoromethyl-substituted electron-poor arenes
that occur with high selectivity for the linear product without
directing groups on the arene. We also show that hydroarylations
occur with internal, acyclic olefins to yield linear alkylarene
products. Experimental mechanistic data provide evidence for
reversible formation of an alkyl-aryl intermediate and rate-
determining reductive elimination to form the carbon-carbon
bond. Labeling studies show that formation of terminal al-
kylarenes from internal alkenes occurs by initial establishment of
an equilibrating mixture of alkene isomers, followed by addition
of the arene to the terminal alkene. Computational (DFT) studies
imply that the aryl C-H bond transfers to a coordinated alkene
without oxidative addition and support the conclusion from exper-
iment that reductive elimination is rate-determining and forms the
anti-Markovnikov product. The reactions are inverse order in α-
olefin; thus the catalytic reaction occurs, in part, because isomeri-
zation creates a low concentration of the reactant α-olefin.
Scheme 1: Development of linear-selective hydroarylation
with unactivated terminal olefins
However, studies to identify more reactive arenes revealed
that 1,3-bis(trifluoromethyl)benzene (1) reacted with 1-octene
to give the linear product in 72% yield and a L:B selectivity
greater than 95:5 (Scheme 1).6 The regioselectivity at the arene
appears to be dominated by steric factors, forming the product
of hydroarylation at the least hindered position of the arene
ring with > 9:1 selectivity.
To avoid formation of side products from hydroarylation of
COD, we examined reactions with precatalysts lacking alkene
ligands. The combination of (TMEDA)Ni(CH2TMS)2 and IPr
or Ni(IPr)2 catalyzed the reaction, but in lower yield and
somewhat reduced L:B selectivity. However, reactions con-
ducted with Ni(IPr)2 as catalyst and 50 mol % NaOtBu addi-
tive formed the addition products in high yield, with high
selectivity for the linear product and for alkylation at the least
hindered position on the arene (L:B > 97:3).6
With these conditions, we examined the reactions of arene 1
with a range of olefins (Chart 1). Hydroarylation of propene
(3), the least sterically biased alkene, resulted in good L:B
selectivity (89:11). This selectivity is much higher than the
1.6:1 regioselectivity reported with previous catalysts.3 The
scope of the reaction encompassed the hydroarylation of steri-
cally bulky cyclohexyl- (4) and tert-butyl-substituted (5) al-
kenes to form anti-Markovnikov products in high yield as a
The hydroarylation of olefins is the most direct method to
prepare alkyl arenes. Classical acid-catalyzed hydroarylations
form branched alkylarene products, whereas metal-catalyzed
hydroarylations could alter the regioselectivity and form linear
alkylarenes. However, current metal-catalyzed hydroarylations
that form linear products require directing groups,1 occur with
specific heteroarenes,2 or occur with a modest preference for
the linear over the branched product.3 The hydroarylation of
alkenes by arenes with high selectivity for the linear products
without directing groups has not been reported.4 We report
nickel-catalyzed additions of the aryl C-H bonds on electron-
poor aryl groups to terminal or internal alkenes to form the
linear alkylarenes with selectivities approaching 20:1. Exper-
imental and computational mechanistic data provide a detailed
view into the factors controlling the rates and regioselectivity.
During our studies on Ni-catalyzed hydrogenolysis of aryl
ethers,5 we discovered that a similar combination of nickel
precursor Ni(COD)2 and IPr carbene ligand (1,3-bis(2,6-
diisopropylphenyl)-2,3-dihydro-1H-imidazole) catalyzed the
addition of benzene to 1-octene to form octylbenzene with a
linear-to-branched selectivity of 95:5. Although the yield was
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single isomer. Reactions conducted with 4-phenyl-1-butene tions occur by addition to the terminal alkene (vide infra), not
1
2
3
4
5
6
7
8
(6) occurred to form the product from intermolecular hy-
droarylation over the potential cyclic product from intramo-
lecular hydroarylation. The reaction also occurred with
strained and unstrained cyclic alkenes (10-13) giving the
products from addition and isomerization of the remaining
alkene to form the conjugated isomer of the product.
The reaction also occurred with olefins bearing a functional
group in the allylic or vinylic position. Both allylic (8) and
vinylic silanes (9), as well as primary (14) and secondary
siloxyethers (15) yielded the linear hydroarylation product.
Furthermore, allylic amines (18-19), acetals (20, masked alde-
hydes) and esters (21) reacted smoothly with excellent L:B
ratio. While vinylic ethers (17) and vinyl silyl ethers (16) gave
low yields, no hydroarylation was observed with allylic alco-
hols or allylic ethers.7,8
by chain walking after insertion of the alkene into a metal-
hydride, as occurs during carbonylations of internal alkenes.10
To understand the mechanism of this remarkably regioselec-
tive hydroarylation, we identified the catalyst resting state and
conducted a series of kinetic studies and isotope labeling stud-
ies. We conducted these studies on the hydroarylation of nor-
bornene to avoid complications from competing isomerization.
The formation of metal complexes in solution was monitored
by NMR spectroscopy using the Ni(IPr)2 possessing a 13C label
at the carbene carbon.11 The 13C NMR resonance of the car-
bene carbon was sensitive to the substituents on Ni.
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Chart 2. Hydroarylation of Internal Acyclic Olefins Gen-
erating Linear Productsa
Chart 1. Hydroarylation of Olefinsa
a
Reactions were performed with 0.15 mmol olefin. Yields and
selectivities are averages from at least two experiments. Yields
are for the major isomer as determined by GC b 30 equiv arene,
combined yield of two linear isomers.
1
Analysis of the reaction mixture by H and 13C NMR spec-
troscopy indicated the presence of a single complex containing
IPr when the conversion was <80%. The structure of the com-
plex was identified as (IPr)Ni(norbornene)2 (24) by independ-
ent synthesis, NMR spectroscopic analysis, and single-crystal
x-ray diffraction (Figure 1). Computational studies by DFT
(vide infra) also suggest that the formation of the bis-olefin
complex is thermodynamically favorable (∆G = -4.1 kcal mol-1
for propene and Ni(IPr)2, A).6
a
Reactions were performed with 0.33-0.5 mmol olefin. Isolated
yields of combined isomers are reported, GC or NMR yields are
in parentheses. L:B ratios were determined by GC. b Reaction was
conducted without NaOtBu c 5 mol% Ni(IPr)2 d 10 mol% Ni(IPr)2
e
f
g
60 ⁰C
Olefin is 1,3-cyclohexadiene
Olefin is 1,3-
cycloheptadiene h Olefin is 1,5-cyclooctadiene.
In addition to the formation of linear alkylarenes from α-
olefins, the nickel complex catalyzes the formation of linear
alkylarenes from internal alkenes. Carbonylation reactions of
internal alkenes to form terminal aldehyde or ester products
are well known,9 but few other reactions of internal alkenes
give terminal products and the reactions of arenes with inter-
nal, acyclic olefins to form linear products are limited to a
single example in low yield.1d Ni(IPr)2 catalyzed the isomeri-
zation and hydroarylation of 3- and 4-octene to form linear
products with yields and selectivities that are comparable to
those from reactions of 1- and 2-octene (Chart 2). These reac-
Figure 1. Synthesis of the resting state, complex 24, and ORTEP
diagram of 24 showing 50% probability thermal ellipsoids. Hy-
drogen atoms are omitted for clarity.
Having identified the resting state of the catalyst, we meas-
ured the reaction orders in substrates and ligand by the method
of initial rates (up to 20% conversion by GC analysis) The
hydroarylation of norbornene by 1 is inverse first order in
norbornene, first order in arene, and zeroth order in ligand.6
To assess whether C-H bond cleavage is irreversible or re-
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Journal of the American Chemical Society
ly, the barrier for direct isomerization from Dn to Fn, with the
versible, we conducted reactions with 5-deuterio-1,3-
1
2
3
4
5
6
7
8
bis(trifluoromethyl)-benzene. The reaction of this labeled
arene with norbornene gave the product from syn addition of
the C-D bond across the alkene (> 98% D incorporation, Fig-
ure 2, A). The kinetic isotope effects on the initial rate of two
side-by-side reactions (conversion to 20%) of the deuterated
and fully protiated arene was only 1.1 ± 0.1.
The hydroarylation of 1-octene by the deuterated arene re-
sulted in complete transfer of the deuterium label predomi-
nantly to the β-position (Figure 2, B). Hydroarylation of the
internal alkene, 4-octene, by 5-D-1 formed a product that also
contained a majority of deuterium at the 2-position of the alkyl
group (Figure 2, C). 12
alkyl group at the base of this structure, is significantly higher
than the barrier for two consecutive isomerizations through En,
with the aryl (TS-DEn) and the IPr (TS-EFn) groups at the
base of the Y-shaped TSs, respectively (Scheme 2). The C-C
bond-forming reductive elimination is computed to occur from
Fn through TS-FGn, and this TS lies at the highest energy on
the catalytic cycle.16 Thus, reductive elimination is the turno-
ver-limiting step of the overall process.17
9
Scheme 2. Proposed catalytic cycle with calculated free
energies in kcal mol-1
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Cn : 18.5
Dn : 14.4
En : 13.4
F3C
CF3
F3C
CF3
F3C
CF3
TS-CDn
21.8
TS-DEn
24.2
H
Ni
Proton
Transfer
IPr Ni
H
Ni
IPr
IPr
TS-DFn
28.8
TS -EFn
- propene
+ arene
Isomerization
CF3
19.3
F3C
F3C
IPr Ni
CF3
TS-FGn
26.4
+ 2
Ni
IPr
F3C
Turnover-
Limiting
Reductive
Elimination
IPr
Ni
B : 0
Gn : -1.3
Fn : 13.3
B' : -10.8
F3C
(B' = the resting state after one turnover)
Our computations indicate that an alternative pathway oc-
curring by oxidative addition of the Ar-H bond, followed by
migratory insertion of the olefin into the nickel-hydride bond
is less favorable (Scheme S1 in Supporting Information).6
The C-C bond-forming reductive elimination is also the
rate-determining step for the formation of the branched isomer
(Scheme S2 in Supporting Information). Consequently the
ratio of linear-to-branched products is determined by the dif-
ference in energy between the two corresponding transition
states for reductive elimination. The calculated value of 1.1
kcal mol-1 for propene translates at 373 K into a ratio of linear
to branched products of 82:18, which agrees well with the
experimentally observed ratio for 3 (Chart 1). The computa-
tions also are consistent with reversible cleavage of the aryl-
H/D bond and hydrometalation of the olefin, which are con-
sistent with the small KIE observed experimentally. Further
consistent with experimental observations, the computational
data indicate that the resting state will be the bis-olefin com-
plex B. Spectroscopic features of an arene complex Gn are
observed only after nearly complete conversion of the olefin.
Two mechanisms were evaluated for the conversion of in-
ternal olefins to give terminal products. First, the olefin could
isomerize through a mechanism unrelated to that of the hy-
droarylation reaction (Figure 3, A). In this case, the nickel
would selectively coordinate the terminal olefin18,19 and favor
hydroarylation of the terminal alkene. Alternatively, chain
walking by a proton transfer from the arene to the internal
olefin would result in a linear alkyl intermediate from an in-
ternal alkene (Figure 3, B).20 Heating 1-octene at 90 ⁰C in the
presence of Ni(IPr)2 resulted in complete conversion of 1-
octene to a combination of (IPr)Ni(1-octene)2 and a mixture of
internal olefins in 30 minutes. Thus, scenario A is kinetically
feasible. Moreover, the results shown in scenario B indicate
that scenario A is relevant to the catalytic reaction. If the reac-
Figure 2. Deuterium incorporation in products of hydroarylation
by deuterated 1. Percentages refer to the integration ratio observed
by 1H- and 2H-NMR spectroscopy of isolated products.
Based on the above observations, we concluded that hy-
droarylation proceeds by a mechanism involving reversible
formation of an alkylnickel aryl species, followed by rate-
limiting C-C bond formation. Prior studies on the hydroaryla-
tion of alkynes suggested that the reactions of alkynes occur
by the transfer of an aryl C-H bond to the bound alkyne with-
out formation of an arylnickel hydride intermediate.13
These experimental mechanistic data and accompanying
conclusions provided the foundation for computational studies
to reveal the mode of C-H bond cleavage and the factors con-
trolling regioselectivity. We computed the reaction of propene
with 1,3-bis-trifluoromethylbenzene. Scheme 2 shows the
Gibbs energies at 373 K (kcal mol-1) with solvent (THF) and
dispersion (D3) corrections calculated by DFT(PBE0).6 The
overall ΔG for this reaction is -10.8 kcal/mol.
These calculations suggest that the C-H bond is cleaved by
transfer of a proton from an η2-C-H bound arene, Cn (Scheme
2), to the bound propene in a H-shift that is similar to the one
described for the hydroarylation of alkynes catalyzed by Ni.13
The resulting alkylnickel aryl intermediate, Dn, which is stabi-
lized by a β-C-H agostic interaction, contains the two hydro-
carbyl groups trans to each other. This complex is computed
to isomerize to a second T-shaped intermediate, Fn, in which
Ni-C(aryl) and Ni-C(alkyl) bonds are mutually cis and able to
undergo C-C bond-forming reductive elimination. This isom-
erization of T-shaped d8-ML3 complexes occurs via Y-shaped
transition states (TSs).14 It is known that the energy of a Y-
shaped d8-ML3 structure increases with the σ-donating proper-
ty of the group at the base of the Y.14b A Y-shaped structure is
also stabilized by a π-donor at the base of the Y.15 Consequent-
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tion proceeds exclusively by scenario A, separate from hy- AC02-05CH11231. YS thanks the SNSF for a Postdoctoral
1
2
3
4
5
6
7
8
droarylation, then the pattern of deuterium incorporation
would be the same as that observed with reactions conducted
with 1-octene (Figure 2, B). If the reaction of the internal
alkene was to occur by a chain-walking pathway, then deuteri-
um would be incorporated at each carbon of the alkyl chain.
We observed deuterium principally in the β- and α-position of
the alkyl chain of the product with 4-octene (Figure 2C). This
result is inconsistent with chain-walking as the major pathway
for alkene isomerization21 and consistent with rapid formation
of a mixture of internal and terminal alkenes (scenario A in
Figure 3).
fellowship. EC and OE thank the CNRS and the MENESR for
funding.
REFERENCES
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(a) Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.;
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E/Z mixtures of 2-, 3-, 4-octene
Ni(IPr)2
+
A
2 (a) Tan, K. L.; Bergman, R. G.; Ellman, J. A. J. Am. Chem. Soc. 2002,
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most reactive
B
F3C
CF3
F3C
CF3
F3C
CF3 F3C
CF3
H
3
(a) Matsumoto, T.; Taube, D. J.; Periana, R. A.; Taube, H.; Yoshida,
H
H
H
H
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IPr Ni
R
Ni
Ni
R
Ni
IPr
IPr
IPr
R
R
H
H
Figure 3. Possible scenarios for the formation of linear prod-
ucts by the hydroarylation of internal olefins.
5 Sergeev, A. G.; Hartwig, J. F. Science 2011, 332, 439.
6 see the Supporting Information for details
7
In conclusion, we report a series of hydroarylations of unac-
tivated olefins with high selectivity for the linear product
without directing groups. These highly regioselective reactions
include those of both terminal and internal alkenes to give
terminal alkylarenes in high yields. Our combined experi-
mental and computational studies reveal several aspects of the
mechanism that make this reaction possible. First, the resting
state of the catalyst during reactions of α-olefins contains two
terminal alkenes, and one alkene dissociates reversibly prior to
the turnover-limiting step; thus, isomerization of the terminal
alkene to an equilibrium mixture of alkenes increases the
reaction rate. Second, the reaction occurs without oxidative
addition to form an unstable nickel hydride intermediate.
Third, the high selectivity results from a lower barrier for
reductive elimination for the linear alkylarenes, rather than a
difference in stabilities of the linear vs. branched alkyl com-
plexes. Studies to understand the detailed mechanisms of
isomerization with nickel complexes and studies to develop
new catalysts for the addition of a wider scope of arenes with
and without concomitant isomerization are ongoing.
For each alkene, different yields were observed with and without the
presence of base. Hence, we report the higher of the two yields. Our
current understanding is that the base inhibits isomerization. Further
studies on the mechanistic effect of the base are ongoing.
8
So far, reactions with electron-neutral to electron-rich arenes contain-
ing typical functional groups, such as nitriles, esters, ketones, amides, and
nitro groups, did not yield any hydroarylation product. An exception is 2-
trilfluoromethylpyridine (see Supporting Information).
9 (a) Seayad, A.; Ahmed, M.; Klein, H.; Jackstell, R.; Gross, T.; Beller,
M. Science 2002, 297, 1676; (b) Jimenez Rodriguez, C.; Foster, D. F.;
Eastham, G. R.; Cole-Hamilton, D. Chem. Commun. 2004, 1720.
10 Orchin, M.; Rupilius, W. Catal. Rev. 1972, 6, 85.
11
Lara, P.; Rivada-Wheelaghan, O.; Conejero, S.; Poteau, R.; Philip-
pot, K.; Chaudret, B. Angew. Chem. Int. Edit. 2011, 50, 12080.
12
No significant differences in deuterium-incorporation were observed
when altering the ratio of arene/olefin from 3:1 to 1:3. No product is
formed in the presence of NaOtBu with trans-4-octene. The incorporation
of deuterium into the α-position is likely to occur from reversible H-shift
of the terminal alkene during isomerization. Calculations showed that the
isomerization of internal olefin following a pathway similar to that from
Cn to En is lower in energy with the H of the arene than with the H of the
isopropyl-group of the ligand. Hence, the deuterium of the arene can be
incorporated into the alkyl chain at various positions.
13
Guihaumé, J.; Halbert, S.; Eisenstein, O.; Perutz, R. N. Organome-
ASSOCIATED CONTENT
tallics 2011, 31, 1300.
14
(a) Komiya, S.; Albright, T. A.; Hoffmann, R.; Kochi, J. K. J. Am.
Supporting Information
Chem. Soc. 1976, 98, 7255; (b) Tatsumi, K.; Hoffmann, R.; Yamamoto,
A.; Stille, J. K. Bull. Chem. Soc. Jpn. 1981, 54, 1857.
Full experimental protocols, characterization data for all new
materials and computational details (list of coordinates of all
calculated species in a .xyz file). This material is available free of
charge via the Internet at http://pubs.acs.org.
15
Riehl, J.-F.; Jean, Y.; Eisenstein, O.; Pélissier, M. Organometallics
1992, 11, 729.
16 Reductive elimination does not occur from En because the aryl group
and the Ni-propyl bond are almost coplanar.
17 Jiang Y.Y.; Li Z.; Shi J. Organometallics 2012, 31, 4356..
18 Hartley, F. R. Chem. Rev. 1973, 73, 163.
AUTHOR INFORMATION
19 Coordination of two internal olefins (2-butene) in the bis-olefin com-
plex is calculated to be less favorable by about 12 kcal mol-1 than coordi-
nation of two terminal olefins (propene).
Corresponding Author
jhartwig@berkeley.edu
20 Vaidya T.; Klimovica K.; LaPointe A. M.; Keresztes I.; Lobkovsky
E. B.; Daugulis O.; Coates G. W. J. Am. Chem. Soc., 2014, 136, 7213
Notes
The authors declare no competing financial interests.
21
Small amounts of deuterium (12% of the total deuterium on the
product) are also observed farther along the alkyl chain. See reference 12.
ACKNOWLEDGMENTS
This work was supported by the Director, Office of Science,
of the U.S. Department of Energy under Contract No. DE-
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Page 5 of 5
Journal of the American Chemical Society
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CF3
CF3
20% Ni(IPr)2
octene
THF, 100 ˚C, 5 h
F3C
F3C
3 equiv
From 1-octene: 65% yield, L:B = >97:3
From 4-octene: 59% yield, L:B = 92:8
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