Rhodium-Catalyzed Enantioselective Defluorinative α-Arylation of Secondary Amides

Article abstract of DOI:10.1002/anie.201808509

We exploited the reactivity of an electronically biased Michael acceptor to perform a defluorinative α-arylation reaction using a chiral diene(L*)-rhodium catalyst. Through this methodology, we are able to obtain various secondary amides, containing a tertiary α-stereocenter and a β,γ-unsaturated gem-difluoro olefin, with excellent enantioselectivities. This methodology addresses the limitations of the previously described α-arylation methods to construct stereo-labile tertiary α-stereocenters. Further investigation of the reaction via in situ ¹⁹F NMR monitoring suggests that the formation of the product leads to the inhibition of the active rhodium catalyst.

Full text of DOI:10.1002/anie.201808509

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Accepted Article
Title: Rhodium-Catalyzed Enantioselective Defluorinative α-Arylation of
Secondary Amides
Authors: Young Jin Jang, Daniel Rose, Bijan Mirabi, and Mark Lautens
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201808509
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Rhodium-Catalyzed Enantioselective Defluorinative α-Arylation of
Secondary Amides
Young Jin Jang, Daniel Rose, Bijan Mirabi and Mark Lautens*[a]
Abstract: We exploited the reactivity of an electronically biased
Michael acceptor to perform a defluorinative α-arylation reaction
using a chiral diene(L*)-rhodium catalyst. Through this methodology,
we are able to obtain various secondary amides, containing a tertiary
reaction is well documented, with pioneering studies described
by the groups of Hartwig, Kündig, Buchwald and Glorius.[7]
Numerous chiral nickel and palladium catalysts have been
described to construct quaternary α-stereocenters. Conversely,
methods to construct stereo-labile tertiary α-stereocenters has
considerably lagged.[8] The origin of this challenge stems from
the comparable acidity of the α-protons in the substrate and in
the resulting product. The strongly basic reaction conditions
promote the epimerization of the α-position, which makes it
challenging to construct tertiary α-stereocenters (Scheme 1d).
Consequently, only products lacking such α-protons or with a
structural bias that inhibits deprotonation can be accessed via
the traditional approach.[9]
α-stereocenter and
a β,γ-unsaturated gem-difluoro olefin, with
excellent enantioselectivities. This methodology addresses the
limitations of the previously described α-arylation methods to
construct stereo-labile tertiary α-stereocenters. Further investigation
of the reaction via in situ 19F NMR monitoring suggests that the
formation of the product leads to the inhibition of the active rhodium
catalyst.
Owing to fluorine’s ability to affect lipophilicity, metabolic
stability and dipole moments of pharmaceutical agents, the
development of methods to incorporate fluorine atoms into an
organic molecule has seen remarkable advances over the past
decade.[1] As a wider array of fluorinated molecules become
available, methods to selectively activate and functionalize
carbon-fluorine bonds have become increasingly valuable.[2]
In this regard, gem-difluoro olefins have proven to be
useful synthetic precursors to a multitude of fluorinated scaffolds.
The electron-deficient nature of these olefins has allowed them
to participate in various stereoselective functionalizations via
Herein, we describe the development of the rhodium-
catalyzed defluorinative α-arylation reaction, granting access to
a novel class of secondary amides containing a tertiary α-
stereocenter and a β,γ-unsaturated gem-difluoro olefin (Scheme
1e). This may serve as an alternative approach to the traditional
palladium- and nickel-catalyzed α-arylation reaction.
transition-metal-catalyzed
methodologies.[3]
These
transformations are versatile methods to access novel classes of
fluorinated organic scaffolds that are otherwise difficult to
synthesize.
Generally, the syntheses of gem-difluoro olefins can be
accomplished through Wittig- or Horner-Wadsworth-Emmons-
type olefination and SN2’ reactions of vinyl trifluoromethyl
compounds (Scheme 1a).[4] Although these methods are
efficient in constructing 1,1-gem-difluoro olefins, development of
methods with milder reaction conditions and broader functional
group tolerance would be beneficial.
In 2016, Hayashi’s group reported the enantioselective
rhodium-catalyzed defluorinative arylation reaction (Scheme 1b).
A
rhodium-mediated arylative β-fluoride elimination was
proposed, leading to enantiomerically enriched gem-difluoro
olefins.[5] We envisioned exploiting this reactivity to achieve an
enantioselective rhodium-catalyzed α-arylation to construct a
potentially stereo-labile tertiary α-stereocenter (Scheme 1c).[6]
The enantioselective transition-metal-catalyzed α-arylation
[a]
Y. J. Jang, D. Rose, B. Mirabi, Professor Dr. M. Lautens
Davenport Research Laboratories, Department of Chemistry,
University of Toronto, Toronto, Ontario, M5S 3H6, Canada.
mlautens@chem.utoronto.ca
Scheme 1. Enantioselective transition-metal-catalyzed α-arylation reactions,
and the proposed rhodium-catalyzed defluorinative α-arylation reaction.
At the outset of our investigation, we set out to
demonstrate our proof of concept on the acrylamide 1a, bearing
a more acidic N–H group versus the α-proton in the resulting
product, in order to minimize epimerization of the α-stereocenter.
The resulting secondary amide would represent a novel class of
difluorinated organic scaffold.
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Initial screening of typical rhodium conjugate addition
conditions quickly led to the optimized conditions for the racemic
transformation (Table 1, entry 1). Screening of various classes
of chiral ligands such as the (R)-BINOL derived phosphoramidite
ligand L1, led to poor yield with moderate enantioselectivity
(Table 1, entry 2). Employing Carreira’s diene L2, furnished the
desired product in comparable enantioselectivity, but with
achieved in a dichloroethane and water mixture as the solvent
(Table 1, entry 7). Subsequent efforts to increase the yield were
challenging, but the use of the preformed rhodium-complex (Rh-
3) (Table 1, entry 8), and increased catalyst loading (Table 1,
entry 9), with additional chiral diene ligand L5 gave better results
(Table 1, entry 10). The use of lithium carbonate led to slightly
higher yield without the erosion of enantioselectivity (Table 1,
entry 11).
With the optimized conditions in hand, we examined the
applicability of our reaction on various substrates. The benzyl-
substituted 2a, the phenyl-substituted 2b, as well as bulky
aliphatic amides 2c and 2d were well tolerated, furnishing the
corresponding products in modest yields and excellent
enantioselectivities. The absolute configuration of 2c was
unambiguously determined through X-ray crystallography, and
the configuration of other substrates is assumed by analogy.
Moreover, heterocycle containing amide 2e was generated in
good yield and excellent enantioselectivity. The tri-substituted
amide 2f was also synthesized, but in lower yield and
enantioselectivity. Conversely, cyclopropyl amide 2g was
obtained in excellent yield and enantioselectivity. Furthermore, a
diverse array of potassium aryl-trifluoroborate salts were
subjected to the reaction conditions. Substitutions on the meta-
Table 1. Optimization Table
[Rh]
L
base
solvent
(4/1)
S.M.
(%)
yield[b]
2a/2a’
ee
2a
1
2
Rh-1
Rh-2
Rh-2
Rh-2
Rh-2
Rh-2
Rh-2
Rh-3
Rh-3
Rh-3
Rh-3
-
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
Li2CO3
diox/H2O
diox/H2O
diox/H2O
diox/H2O
diox/H2O
diox/H2O
DCE/H2O
DCE/H2O
DCE/H2O
DCE/H2O
DCE/H2O
<5
45
<5
53
17
61
41
55
15
<5
<5
84 / 13
15 / 23
41 / 27
23 / 8
-
L1
L2
L3
L4
L5
L5
-
56
-50
78
90
90
94
ND
98
98
98
3
4
5
10 / 67
31 / <5
40 / <5
30 / <5
60 / <5
68 / <10
74 / <5
6
7
8
9[a]
10[a]
11[a]
-
L5
L5
Enantiomeric excess was determined by HPLC using chiral stationary phase
column, and yields, S.M. and ee are reported in percentages. [a] 10 mol % of
[Rh] [b] NMR yields determined from crude 1H NMR spectra, using 1,3,5-
trimethoxybenzene as the internal standard. [c] See Supporting information for
detailed reaction conditions and characterization data.
Figure 1. Substrate scope of the enantioselective defluorinative α-arylation
reaction. KOH (2 equiv) was used as base and the reaction was conducted for
30 h unless otherwise indicated. See supporting information for detailed
reaction conditions. Enantiomeric excess was determined by HPLC. [a] 2
equivalents of Li2CO3 was used and the reaction was carried out for 24 h. [b] 2
equivalents of K2CO3 was used and the reaction was carried out for 24 h.
improved yield (Table 1, entry 3). Upon switching to Hayashi’s
diene L3, Ph-bod* (Table 1, entry 4), we observed superior
enantioselectivity, albeit in low yield. Further screening of chiral
diene ligands derived from α-phellandrene (L4, L5) gave
improved results (Table 1, entries 5,6), with the best outcome
and para- positions were well tolerated (2h-n, 2p-q, 2s-2z),
giving modest yields and comparable enantioselectivities.
Interestingly, reactions with cyclopropylamide gave consistently
higher yields compared to other amides. In comparison, the
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reaction of ortho-substituted aryl trifluoroborate salts (2o, 2r),
independent of their electronic properties, led to lower yields, but
with excellent enantioselectivities. Functional groups such as
primary alcohol (2w) and mono-substituted olefin (2x) were well
tolerated with excellent enantioselectivities.
Scheme 2. Probing the effects of different electron withdrawing groups.
To probe the effects of the electron withdrawing group on
the reaction outcome, β-trifluoromethyl substituted acrylates and
acrylones were also investigated. Using the acrylate (Scheme
2a), minimal amounts of the desired α-arylated product were
observed accompanied by a significant amount of the 1,4-
conjugate adduct. Similarly, acrylone was shown to be too
reactive towards 1,4-addition with the hydration of the double
bond being observed as the major product (Scheme 2b).[10]
Overall, less electron withdrawing amides are favoured in the
defluorinative α-arylation reaction.
Figure 2. Fluorobenzene was used as the internal standard, see supporting
information for additional plots and detailed reaction procedures.
indicated by the dotted arrows, should be identical, and
complete overlay of the two graphs of time adjusted run 1 and
run 2 should be observed.
Additionally,
a
product inhibition experiment was
conducted (Scheme 3-II). In this experiment, 35 mol % of
product 2a (98% ee) was added at time 0, and the reaction rate
was compared to the ‘same excess’ experiment (Figure 2b). At
the time point indicated by the dotted arrows, not only are the
temporal concentrations of 1a, 1a’ identical, but also the
temporal concentration of 2a is matched in both experiments.
Comparing the rates of both runs at this time point and onwards,
indicates that the catalyst is sensitive to product inhibition.
Furthermore, clear deviation of the two plots is observed with
time (t > 5 h), suggesting that the byproducts generated,
excluding 2a, help to alleviate product inhibition of the active
catalyst (indicated by higher consumption of starting material in
run 2). Although the exact nature of this phenomenon is unclear,
the different reaction rates observed between the two runs
(figure 2b), suggests that the product 2a chelates to the rhodium
catalyst, potentially leading to the formation of an off-cycle ML1L2
(L1 = L5, L2 = product*) species that is in equilibrium with the
active catalyst.[12] We speculate that the boron salts generated
Scheme 3. Product inhibition experiments monitored via 19F NMR.
Incomplete conversion leading to low yields was observed
in our studies. This led us to speculate the potential for catalyst
deactivation. To gain additional insight, the ‘same excess’
protocol developed by Blackmond was conducted (Scheme 3-
I).[11] Two experiments I (Run 1) and I’’ (Run 2) have different
initial concentrations of 1a and 1a’, but the difference in their
temporal concentrations are identical (‘same excess’ defined as
[1a’]0 – [1a]0). A comparison of the reaction rates of the two runs
at the time point indicated by the dotted arrows, where the
concentrations of 1a and 1a’ are identical in both runs 1 and 2,
supports the proposal that the accumulation of product leads to
catalyst deactivation (Figure 2a). This may be due to either
catalyst decomposition over time or the catalyst could be
sensitive to product inhibition.[11] Conversely, in the absence of
catalyst deactivation, the observed reaction rate at the time point
from
the
hydrolysis/transmetalation
of
potassium
aryltrifluoroborate salt,[13] help to shift the equilibrium towards the
active catalyst leading to a more efficient reaction.
To demonstrate the utility of the products, derivatization
studies were conducted as shown in Scheme 4. Employing the
nickel-catalyzed hydrodefluorination methodology developed by
Cao,[14] the gem-difluoro olefin was fully reduced to afford 3ca in
good yields. Furthermore, the coupling of gem-difluorides with
simple Grignard reagent was realized under nickel catalysis,[15]
furnishing the desired product 3cb in good yield with no loss in
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information for detailed reaction conditions.
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In conclusion, we have developed an enantioselective
rhodium-catalyzed defluorinative α-arylation reaction. Through
the development of our methodology, we are able to access
various secondary amides, containing a tertiary α-stereocenter
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and
obtained exhibit thermodynamic stability towards isomerization
and are novel class of fluorinated molecules. Further
a β,γ-unsaturated gem-difluoro olefin. The products
a
derivatization studies are underway to access enantiomerically
enriched fluorinated compounds.
Acknowledgements
We thank the University of Toronto, Alphora Research, Inc., and
the Natural Sciences and Engineering Research Council
(NSERC) for financial support. We thank Dr. Jack Sheng and
the NMR staff for their assistance, Dr. Alan Lough for obtaining
all X-ray crystal structures, and Professor Mark Taylor for helpful
suggestions and guidance with the “same excess” kinetic
studies. Dr. Ivan Franzoni, H. Xiao and A. Yen are thanked for
fruitful discussions throughout the project. Actelion and Johnson
Matthey are thanked for their donation of the Ph-bod* precursor
and subsidy with the rhodium complexes, respectively.
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Keywords: Defluorinative Arylation • Asymmetric Catalysis •
Rhodium Catalysis
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Entry for the Table of Contents
Layout 2:
COMMUNICATION
Young Jin Jang, Daniel Rose, Bijan
Mirabi, Mark Lautens*
Page No. – Page No.
Rhodium-Catalyzed Enantioselective
Defluorinative α-Arylation of
Secondary Amides
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