Site-selective C-H/C-N activation by cooperative catalysis: Primary amides as arylating reagents in directed C-H arylation

Article abstract of DOI:10.1021/acscatal.7b02540

Direct C-H arylation of nonacidic C(sp)-H bonds with primary amides as arylating reagents via highly chemoselective C-H/C-N/C-C cleavages has been accomplished for the first time. The key to the success is the cooperative combination of rhodium(I) catalys

Full text of DOI:10.1021/acscatal.7b02540

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Letter
Site-Selective C–H/C–N Activation by Cooperative Catalysis:
Primary Amides as Arylating Reagents in Directed C–H Arylation
Guangrong Meng, and Michal Szostak
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b02540 • Publication Date (Web): 11 Sep 2017
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Site-Selective C–H/C–N Activation by Cooperative Catalysis: Prima-
ry Amides as Arylating Reagents in Directed C–H Arylation
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Guangrong Meng, and Michal Szostak*
Department of Chemistry, Rutgers University, 73 Warren Street, Newark, New Jersey 07102, United States
Supporting Information
ABSTRACT: Direct C–H arylation of non-acidic C(sp2)–H bonds with primary amides as arylating reagents via highly
chemoselective C–H/C–N/C–C cleavages has been accomplished for the first time. The key to the success is the coopera-
tive combination of rhodium(I) catalysis and Lewis base catalysis, which can promote activation of inert C–N bonds in
generic primary amides after selective N-tert-butoxycarbonyl activation in a highly efficient manner. Notably, this report
constitutes the first biaryl synthesis enlisting common primary amides by N–C bond activation. This report also discloses
for the first time the potential of generic, acyclic secondary amides as arylating reagents in directed C–H arylation. Con-
sidering the fundamental importance of biaryls and the key role of primary amides in organic synthesis, we expect that
this concept by synergistic catalysis for aryl–aryl coupling will unlock broad catalytic applications.
KEYWORDS: C–H activation, C–N activation, amides, arylation, arylating reagents, cooperative catalysis
Amides are among the most important and prevalent
functional groups in drug discovery, polymers and chemi-
cal industry.1 While numerous methods for the function-
alization of amide bonds by selective N–C cleavage2–6 have
been developed utilizing amide Nlp to C=O ground-state
destabilization7,8 (barrier to rotation, amide bond reso-
nance in primary amides of 15-20 kcal/mol), cross-
coupling of generic primary amides remains a challenging
task. Despite the prevalence of primary amides as funda-
mental building blocks in pharmaceuticals, agrochemicals
and electronic materials,9,10 chemical methods that induce
site-selective N–C insertion/decarbonylation and catalyti-
cally generate aryl electrophiles have remained elusive to
direct catalytic pathways.4–6
Transition-metal-catalyzed C–H activation has been es-
tablished as a very attractive method for the preparation
of biaryl motifs.11 Invention of new methods and arylating
reagents for the site-selective construction of biaryls uti-
lizing non-acidic C(sp2)–H bonds has a wide-ranging im-
pact on the field.12–14 Recently, a number of elegant pro-
cesses for the selective activation/C–H cross-coupling of
C(sp2)–O bonds has been developed.15 Significant advanc-
es have been made in the development of biaryl synthesis,
involving C–X and C–C cleavage that enable a range of
functional groups to selectively participate in the assem-
bly of biaryls.16,17 Herein, we describe a new concept for
aryl–aryl coupling that utilizes primary amides as ary-
lating reagents via highly chemoselective C–N/C–C/C–H
cleavages in the absence of oxidants, enabled by the un-
ion of cooperative rhodium(I) and Lewis base catalysis.18
Notably, the method represents the first biaryl synthesis
enlisting common primary amides by N–C bond activa-
tion (Figure 1).4–6 This reaction manifold differs from the
direct acyl Negishi cross-coupling using Ni catalysis,
wherein metal insertion proceeds directly into the amide
N–C bond.8e The catalytic cooperative strategy has great
potential in overriding the inherent reactivity18c and may
pave the way for the generic application of common acy-
clic amides9,10 as aryl donor components in the synthesis
of aryl–aryl motifs.12
Notable features of our findings include: (1) the first use
of common primary amides as arylating reagents via re-
dox-neutral decarbonylation; (2) cooperative catalytic
system to selectively access aryl metal intermediates.
Based on our previous work in electrophilic activation
of amides and metal-catalysis, we propose the mechanism
shown in Figure 2. Initial amide transacylation enabled by
N,N-diacylation of the amide bond19 (ER = 7.6 kcal/mol)
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with an appropriate Lewis base produces acylammonium
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the N–carbamate, which is a common side reaction with
nucleophilic Ni(0) and Pd(0)-catalytic systems,2–6 thus
resulting in a broadly applicable process.
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intermediate (nucleophilic cycle). In a simultaneous or-
ganometallic cycle, Rh(I), undergoes selective oxidative
addition into weak acylammonium bond20,21 to generate a
highly reactive acyl-Rh(III) intermediate. The feasibility of
this proposed manifold heavily relies on the propensity of
the acyl-Rh(III) intermediate to undergo controlled de-
carbonylation.22 The subsequent chelation-directed ortho-
C–H arylation by aryl–Rh(III)23 gives diarylrhodium(III),
releasing the Lewis base catalyst. The diarylrhodium(III)
undergoes reductive elimination to generate the biaryl C–
The reaction conditions were first optimized for the
cross-coupling of N,N-di-Boc-activated amide (1) with
benzo[h]quinoline as the model substrate for investiga-
tion (Table 1, entry 1). The optimized conditions utilize
[Rh(cod)Cl]2 (5 mol%), n-Bu3N (30 mol%), H2O (1.5 equiv)
in toluene at 150 °C, affording the desired product in
quantitative yield. Several points should be noted: (1) all
N,N-di-Boc activated amides are prepared directly in one-
step from the corresponding benzamides, including sub-
strates with Lewis basic sites.25 This represents a substan-
tial departure form the cross-coupling of other types of
amides that have been largely thus far limited to the cou-
pling of less common tertiary amides that are ultimately
Table 1. Optimization of the Reaction Conditionsa
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entry
1
catalyst
nucleophile additive yield (%)b
[Rh(cod)Cl]2
[Rh(cod)2]BF4
[Rh(C2H4)2Cl]2
[Rh(CO)2Cl]2
RhCl(PPh3)3
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
Bu3N
Bu3N
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
-
>98
70
53
35
2
Figure 1. Decarbonylative cross-coupling of amides by N–C bond
activation: current state-of-the-art and present work.
3
Bu3N
4
Bu3N
5
Bu3N
<5
97
29
<5
18
6
Et3N
7
DIEA
isoquinoline
pyridine
quinoline
DMAP
Bu3N
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9
10
11
73
<5
59
20
19
12
13
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15
16c
17d
18
-
H2O
-
-
K2CO3
Bu3N
-
<5
20
79
98
H2O
H2O
H3BO3
Bu3N
Bu3N
aConditions: 1 (1.0 equiv), amide (1.5 equiv), catalyst (5 mol%), L.B.
(30 mol%), additive (1.5 equiv), toluene (0.25 M), 150 °C, 15 h. bGC/1H
NMR yields. cBu3N (1.0 equiv). dH2O (3.0 equiv). L.B. = Lewis base.
Figure 2. Proposed mechanism for site-selective C–H arylation with
common 1° amides as arylating reagents by cooperative catalysis.
H activation product and releases the Rh(I) catalyst to
complete the cycle. Given the marked increase in electro-
philicity of the N–C(O) bond following selective N-tert-
butoxycarbonyl activation,19 we presumed that the nucle-
ophilic capture of the amide bond would be facile. Proto-
nating the carbonyl group of the N–carbamate would fur-
ther increase the propensity of the amide bond for metal
insertion.24 Finally, the mild conditions associated with
Rh(I)-catalysis23 would obviate the undesired cleavage of
derived from carboxylic acids or aroyl chlorides2–6 (cf.
ubiquitous primary amides).9,10 (2) The cooperative cata-
lytic cycle bypasses the direct metal insertion into the
amide bond, thus providing a powerful catalytic approach
that can be triggered by complementary reactivity to the
conventional activation.18 (3) The high chemoselectivity of
the process toward decarbonylation bodes well for the
development of direct arylation reactions with other elec-
2
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With our newly developed arylation in hand the sub-
trophiles,26 and hinges upon high capability of Rh(I) to
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facilitate decarbonylation.
strate scope of this deamidative C–C/C–H coupling was
investigated. As shown in Scheme 1, a wide range of elec-
tronically-diverse amides can be employed in this trans-
formation (3a-3d). Notably, bulky ortho-substituted am-
ides can be tolerated, albeit in slightly diminished yields
(3e-3f). Of particular note, the latter substrate directly
utilizes 2-ethoxybenzamide (anti-inflammatory drug),27
thus highlighting the capacity of the method to engage
common substrates bearing primary amide bond. Particu-
larly noteworthy is the functional group tolerance of this
method, including fluorides (3g), chlorides (3h), bromides
(3i), esters (3j), anilines (3k), and nitriles (3l) that would
be problematic with Grignard reagents. Meta-substitution
is well-tolerated (3m-3n). Furthermore, heterocycles (3o)
and polyarenes (3p) are compatible with the reaction
conditions, despite their capacity to undergo deamidative
decomposition. The arylation using 3-pyridyl amide con-
taining additional basic nitrogen proceeds in unoptimized
49% yield (not shown). The scope with respect to the di-
recting
Selected key optimization results are presented in Table
1. Various catalysts were tested, and [Rh(cod)Cl]2 showed
the best activity (entries 1-5). Of note, Wilkinson’s cata-
lyst showed poor reactivity in the coupling. Other Lewis
bases can also be used; however, n-Bu3N provided con-
sistently the best results (entries 6-11). Water acts as an
essential additive in this coupling (entries 12-14). Water
can be substituted with H3BO3 without a significant de-
crease in the reaction efficiency (entries 18). We hypothe-
size that the amide bond is activated by switchable O-/O-
coordination of the N–carbamate.24 The inclusion of an
inorganic base, K2CO3, inhibits the reaction (entry 15 cf.
14).16i As expected, no product formation is observed in
the absence of rhodium catalyst and minimal product
formation is
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Scheme 1. C–H Arylation of Benzo[h]quinoline with
Amides by Cooperative Catalysis: Amide Variationa,b
Scheme 2. C–H Arylation with Amides by Cooperative
Catalysis: Variation of 2-Phenylpyridinea,b
aConditions: 1 (1.0 equiv), amide (1.5 equiv), [Rh(cod)Cl]2 (5 mol%),
Bu3N (30 mol%), H2O (1.5 equiv), toluene (0.25 M), 150 °C, 15 h. I-
b
aConditions: 1 (1.0 equiv), amide (1-3 equiv), [Rh(cod)Cl]2 (5 mol%),
solated yields. See SI for details.
b
Bu3N (30 mol%), H2O (1.5 equiv), toluene (0.25 M), 150 °C, 15 h. I-
observed in the absence of Lewis base (<20%) (entries 13-
14). The optimized stoichiometry is critical to match the
efficiency of both cycles (entries 16-17). Finally, it should
be noted that the process is highly practical; the reaction
can be conduced in the presence of ambient air in excel-
lent yields.
solated yields. See SI for details. pym = 2-pyrimidyl; py = 2-pyridyl.
group component was next evaluated (Scheme 2). Typi-
cally, excess of the amide was used, resulting in double C–
H arylation (3q). This highly efficient process results in
selective breaking of 6 different bonds (96.1% efficiency
per bond). The example with stoichiometric amount (3r)
illustrates that monoarylation is possible with high
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Scheme 3. Sequential Cross-Couplinga
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aConditions: a) I2, NaIO4, H2SO4, 23 °C; b) Boc2O, Et3N, CH2Cl2, 23 °C; c) Pd(OAc)2, PhB(OH)2, Na2CO3, EtOH:H2O, 23 °C; d) standard conditions.
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Scheme 4. C–H Arylation with Common Secondary
Amides by Cooperative Catalysis
The potential of primary benzamides to serve as a di-
recting group was demonstrated in the sequential meta-
iodination, Suzuki cross-coupling/C–H arylation (Scheme
3). Importantly, Suzuki cross-coupling could be readily
performed in the presence of the electrophilic N,N-di-Boc
moiety, allowing for a strategically valuable disconnection
akin to Weinreb amides,28 but via a decarbonylative
pathway.
Intriguingly, although these reactions conditions were
optimized for N,N-di-Boc-benzamides, we found that
acyclic N,N-Ph/Boc and N,N-Ph/Ts amides that are readi-
ly prepared from common secondary2,4c amides under-
went arylation in 49-76% yields (Scheme 4). Importantly,
this observation shows the potential of cooperative cata-
lytic strategy to engage common secondary acyclic amides
as arylating reagents for directed C–H arylation.
Several studies were performed to gain insight into the
mechanism (Scheme 5). (1) Intermolecular competition
experiments between differently substituted amides (R =
4-MeO/4-CF3) revealed that the coupling is relatively in-
sensitive to the electronics of electrophile (1:1). (2) Further
competition experiments with differently substituted 2-
phenylpyridines revealed the electron-rich arenes are in-
herently more reactive (R = 4-MeO/4-CF3, 4:1). (3) The
following order of reactivity of amide electrophiles has
been established: N,N-Boc2 ≈ N,N-Ts/Ph >> N,N-Boc/Ph.
In addition, anilides (N,N-alkyl/Ph) and N,N-dialkyl am-
ides are recovered unchanged from these conditions, at-
testing to the potential of the method in chemoselective
synthesis and consistent with the electrophilicity of the
amide bond undergoing N–C cleavage.19 (4) Deuterium
incorporation experiments revealed reversibility of the C–
H activation step at the ortho-position of 1a. (5) A TON of
480 in Rh in the arylation of 1a with 2a has been deter-
mined, showing highly efficient catalysis. Overall, these
mechanistic findings strongly support reversible C–H
functionalization by electrophilic substitution pathway.15e
Further studies to elucidate the mechanism are ongoing.
In summary, we have developed the first method for ar-
ylation of non-acidic C(sp2)–H bonds with primary am-
ides as the arylating reagent. The key to the successful
development is the use of cooperative rhodium(I) cataly-
sis and Lewis base catalysis, which can promote activation
of inert C–N bonds in ubiquitous primary amides after
selective N-tert-butoxycarbonyl activation in a highly effi-
cient manner by an orchestrated sequence of C–N, C–C
and C–H cleavages. Considering that primary amides are
among the most important amide derivatives in small
organic molecules and prevalent intermediates in phar-
maceuticals and biologically active materials, we expect
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Scheme 5. Mechanistic Studies
selectivity. Substrates bearing para- (3s-3u) and meta-
substituents (3v) on the 2-phenylpyridine component
were successfully coupled in good yields. The more steri-
cally-demanding ortho-methyl substrate successfully
coupled, albeit in lower yield (3w). Conversely, ortho-
substitution on the pyridine was well-tolerated, resulting
in high selectivity for monoarylation (3x). Furthermore,
substrates bearing other heterocycles, such as pyrimidine
(3y), pyrrole (3z), indole (3aa) and benzothiophene (3ab)
were successfully coupled with amides to afford the biaryl
products in good to excellent yields.
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(6) For representative tandem coupling, see: Walker, J. A.;
that this study will be of great interest. Equally im-
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Vickerman, K. L.; Humke, J. N.; Stanley, L. M. J. Am. Chem. Soc.
2017, 139, 10228-10231 and references cited therein.
portantly, this process provides a novel method for gener-
ating aryl electrophiles, and may unlock a broad range of
arylations by synergistic catalysis mechanisms. Studies
toward expanding the reaction scope to other precursors
as well as on further developments of C–N activation
technologies are actively pursued in our laboratory and
will be reported in due course.
(7) For classic studies on amide destabilization in bridged lac-
tams, see: (a) Tani, K.; Stoltz, B. M. Nature 2006, 441, 731-734. (b)
Greenberg, A.; Venanzi, C. A. J. Am. Chem. Soc. 1993, 115, 6951-
6957. (c) Aubé, J. Angew. Chem. Int. Ed. 2012, 51, 3063-3065.
(8) For pertinent studies on amide destabilization in N–C
cross-coupling, see: (a) Szostak, R.; Shi, S.; Meng, G.; Lalancette,
R.; Szostak, M. J. Org. Chem. 2016, 81, 8091-8094. (b) Pace, V.;
Holzer, W.; Meng, G.; Shi, S.; Lalancette, R.; Szostak, R.; Szostak,
M. Chem. Eur. J. 2016, 22, 14494-14498. (c) Szostak, R.; Meng, G.;
Szostak, M. J. Org. Chem. 2017, 82, 6373-6378. (d) See, ref. 1c. (e)
For acyl-Negishi coupling using N,N-Boc2-amides, see: Shi, S.;
Szostak, M. Org. Lett. 2016, 18, 5872-5875.
ASSOCIATED CONTENT
Supporting Information
Procedures and analytical data. This material is available free
of charge via the Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Author
(9) (a) Roughley, S. D.; Jordan, A. M. J. Med. Chem. 2011, 54,
3451-3479. (b) Kaspar, A. A.; Reichert, J. M. Drug Discov. Today
2013, 18, 807-817. (c) Marchildon, K. Macromol. React. Eng. 2011,
5, 22-54. (d) Chen, Y.; Turlik, A.; Newhouse, T. J. Am. Chem. Soc.
2016, 138, 1166-1169.
michal.szostak@rutgers.edu
ACKNOWLEDGMENT
Rutgers University and the NSF (CAREER CHE-1650766) are
gratefully acknowledged for support. The Bruker 500 MHz
spectrometer used in this study was supported by the NSF-
MRI grant (CHE-1229030).
(10) (a) Larock, R. C. Comprehensive Organic Transformations;
Wiley: New York, 1999. (b) Zabicky, J. The Chemistry of Amides;
Interscience: New York, 1970.
(11) Select reviews on C–H activation: (a) Yu, J. Q. Science of
Synthesis: Catalytic Transformations via C–H Activation; Thieme:
Stuttgart, 2015. (b) Chen, Z.; Wang, B.; Zhang, J.; Yu, W.; Liu, Z.;
Zhang, Y. Org. Chem. Front. 2015, 2, 1107-1295. (c) Daugulis, O.;
Roane, J.; Tran, L. D. Acc. Chem. Res. 2015, 48, 1053-1064. (d)
Miao, J.; Ge, H. Eur. J. Org. Chem. 2015, 7859-7868. (e) Rossi, R.;
Bellina, F.; Lessi, M.; Manzini, C. Adv. Synth. Catal. 2014, 356, 17-
117. (f) Engle, K. M.; Mei, T. S.; Wasa, M.; Yu, J. Q. Acc. Chem.
Res. 2012, 45, 788-802. (g) Yamaguchi, J.; Yamaguchi, A. D.;
Itami, K. Angew. Chem. Int. Ed. 2012, 51, 8960-9009. (h) Yeung,
C. S.; Dong, V. M. Chem. Rev. 2011, 111, 1215-1292. (i) Lyons, T.;
Sanford, M. Chem. Rev. 2010, 110, 1147-1169.
REFERENCES
(1) (a) Greenberg, A.; Breneman, C. M.; Liebman, J. F. The Am-
ide Linkage: Structural Significance in Chemistry, Biochemistry
and Materials Science; Wiley-VCH: New York, 2003. (b) Pattabi-
raman, V. R.; Bode, J. W. Nature 2011, 480, 471-479. (c) Ruider, S.;
Maulide, N. Angew. Chem. Int. Ed. 2015, 54, 13856-13858.
(2) For reviews on N–C functionalization, see: (a) Takise, R.;
Muto, K.; Yamaguchi, J. Chem. Soc. Rev. 2017, DOI:
10.1039/c7cs00182g. (b) Meng, G.; Shi, S.; Szostak, M. Synlett
2016, 27, 2530-3540. (c) Liu, C.; Szostak, M. Chem. Eur. J. 2017, 23,
7157-7173.
(12) (a) Hussain, I.; Singh, T. Adv. Synth. Catal. 2014, 356, 1661-
1696. (b) Modern Arylation Methods, Burke, A. J.; Marques, C. S.,
Eds.; Wiley-VCH: Weinheim, 2015.
(3) (a) Science of Synthesis: Cross-Coupling and Heck-Type Re-
actions, Molander, G. A.; Wolfe, J. P.; Larhed, M., Eds.; Thieme:
Stuttgart, 2013. (b)Metal-Catalyzed Cross-Coupling Reactions and
More, de Meijere, A.; Bräse, S.; Oestreich, M., Eds.; Wiley: New
York, 2014. (c) New Trends in Cross-Coupling; Colacot, T. J., Ed.;
The Royal Society of Chemistry: Cambridge, 2015.
(13) For a comprehensive review on C–H arylation with organ-
ometallics, see: Giri, R.; Thapa, S.; Kafle, A. Adv. Synth. Catal.
2014, 356, 1395-1411.
(14) For a recent C–H arylation of primary amines, see: Liu, Y.;
Ge, H. Nat. Chem. 2017, 9, 26-32.
(4) For representative acyl coupling, see: (a) Hie, L.; Nathel, N.
F. F.; Shah, T. K.; Baker, E. L.; Hong, X.; Yang, Y. F.; Liu, P.;
Houk, K. N.; Garg, N. K. Nature 2015, 524, 79-83. (b) Meng, G.;
Szostak, M. Org. Lett. 2015, 17, 4364-4367. (c) Lei, P.; Meng, G.;
Szostak, M. ACS Catal. 2017, 7, 1960-1965. (d) Meng, G.; Lei, P.;
Szostak, M. Org. Lett. 2017, 19, 2158-2161. (e) Amani, J.; Alam, R.;
Badir, S.; Molander, G. A. Org. Lett. 2017, 19, 2426-2429. (f) Ni, S.;
Zhang, W.; Mei, H.; Han, J.; Pan, Y. Org. Lett. 2017, 19, 2536-2539.
(g) Lei, P.; Meng, G.; Shi, S.; Ling, Y.; An, J.; Szostak, R.; Szostak,
M. Chem. Sci. 2017, 8, 6525-6530 and references cited therein.
(5) For representative decarbonylative coupling, see: (a)
Meng, G.; Szostak, M. Angew. Chem. Int. Ed. 2015, 54, 14518-
14522. (b) Shi, S.; Meng, G.; Szostak, M. Angew. Chem. Int. Ed.
2016, 55, 6959-6953. (c) Meng, G.; Szostak, M. Org. Lett. 2016, 18,
796. (d) Dey, A.; Sasmai, S.; Seth, K.; Lahiri, G. K.; Maiti, D. ACS
Catal. 2017, 7, 433-437. (e) Yue, H.; Guo, L.; Liao, H. H.; Cai, Y.;
Zhu, C.; Rueping, M. Angew. Chem. Int. Ed. 2017, 56, 4282-4285.
(f) Yue, H.; Guo, L.; Lee, S. C.; Liu, X.; Rueping, M. Angew. Chem.
Int. Ed. 2017, 56, 3972-3976. (g) Srimontree, W.; Cha-
tupheeraphat, A.; Liao, H. H.; Rueping, M. Org. Lett. 2017, 19,
3091-3094. (h) Shi, S.; Szostak, M. Org. Lett. 2017, 19, 3095-3098
and references cited therein.
(15) Ni: (a) Amaike, K.; Muto, K.; Yamaguchi, J.; Itami, K. J.
Am. Chem. Soc. 2012, 134, 13573-13576. (b) Muto, K.; Yamaguchi,
J.; Lei, A.; Itami, K. J. Am. Chem. Soc. 2013, 135, 16384-16387. (c)
Muto, K.; Hatakeyama, T.; Yamaguchi, J.; Itami, K. Chem. Sci.
2015, 6, 6792-6798. Co: (d) Song, W.; Ackermann, L. Angew.
Chem. Int. Ed. 2012, 51, 8251-8254. Rh: (e) Tobisu, M.; Yasui, K.;
Aihara, Y.; Chatani, N. Angew. Chem. Int. Ed. 2017, 56, 1877-1880.
(16) Select examples: Halides/pseudohalides: (a) Kametani, Y.;
Satoh, T.; Miura, M.; Nomura, M. Tetrahedron Lett. 2000, 41,
2655-2659. (b) Daugulis, O.; Zaitsev, V. G.; Angew. Chem. Int. Ed.
2005, 44, 4046-4048. (c) Berman, A. M.; Lewis, J. C.; Bergman, R.
G.; Ellman, J. A. J. Am. Chem. Soc. 2008, 130, 14926-14927. (d)
Kim, M.; Kwak, J.; Chang, S. Angew. Chem. Int. Ed. 2009, 48,
8935-8939. (e) Ackermann, L.; Althammer, A.; Born, R. Angew.
Chem. Int. Ed. 2006, 45, 2619-2622. (f) Roger, J.; Doucet, H. Org.
Biomol. Chem. 2008, 6, 169-174. Organometallics: (g) Sun, C. L.;
Li, B. J.; Shi, Z. J. Chem. Commun. 2010, 46, 677-685. Arenes: (h)
Zhao, X.; Yeung, C. S.; Dong, V. M. J. Am. Chem. Soc. 2010, 132,
5837-5844. Aroyl halides: (i) Zhao, X.; Yu, Z. J. Am. Chem. Soc.
2008, 130, 8136-8137. Anhydrides: (j) Jin, W.; Yu, Z.; He, W.; Ye,
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W.; Xiao, W. J. Org. Lett. 2009, 11, 1317-1320. (k) Pan, F.; Lei, Z.
1
2
3
4
5
6
7
8
Q.; Wang, H.; Li, H.; Sun, J.; Shi, Z. J. Angew. Chem. Int. Ed. 2013,
52, 2063-2067. Aldehydes: (l) Shuai, Q.; Yang, L.; Guo, X.; Basle,
O.; Li, C. J. J. Am. Chem. Soc. 2010, 132, 12212-12213.
(17) For pertinent examples of decarboxylative cross-coupling,
see: (a) Gooßen, L. J.; Deng, G.; Levy, L. M. Science 2006, 313,
662-664. (b) Gooßen, L. J.; Rodriguez, N.; Melzer, B.; Linder, C.;
Deng, G.; Levy, L. M. J. Am. Chem. Soc. 2007, 129, 4824-4833. (c)
Wei, Y.; Hu, P.; Zhang, M.; Su, W. Chem. Rev. 2017, 117, 8864-
8907.
9
(18) Select reviews on cooperative catalysis: (a) Peters, R. Co-
operative Catalysis: Designing Efficient Catalysts for Synthesis;
Wiley-VCH: 2015. (b) Du, Z.; Shao, Z. Chem. Soc. Rev. 2013, 42,
1337-1378. (c) Allen, A. E.; MacMillan, D. W. C. Chem. Sci. 2012, 3,
633-658.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(19) Davidsen, S. K.; May, P. D.; Summers, J. B. J. Org. Chem.
1991, 56, 5482-5485.
(20) (a) Blakey, S. B.; MacMillan, D. W. C. J. Am. Chem. Soc.
2003, 125, 6046-6047. (b) Buszek, K. R.; Brown, N. Org. Lett. 2007,
9, 707-710.
(21) Reviews on acyl-metal intermediates: (a) Gooßen, L. J.;
Rodriguez, N.; Gooßen, K. Angew. Chem. Int. Ed. 2008, 47, 3100-
3120. (b) Dzik, W. I.; Lange, P. P.; Gooßen, L. J. Chem. Sci. 2012, 3,
2671-2678.
(22) Johnson, J. B.; Rovis, T. Acc. Chem. Res. 2008, 41, 327-338.
(23) Colby, D. A.; Bergman, R. G.; Ellman, J. A. Chem. Rev.
2010, 110, 624-655.
(24) Cox, C.; Lectka, T. Acc. Chem. Res. 2000, 33, 849-858.
(25) See the Supporting Information.
(26) Bera, M.; Agasti, S.; Chowdhury, R.; Mondal, R.; Pal, D.;
Maiti, D. Angew. Chem. Int. Ed. 2017, 56, 5272-5276 and refer-
ences cited therein.
(27) Lemke, T. L.; Williams, D. A. Foye’s Principles of Medici-
nal Chemistry, Lippincott: Philadelphia, 2013.
(28) Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815-
3818.
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