Cross-Coupling of Amides with Alkylboranes via Nickel-Catalyzed C-N Bond Cleavage

Article abstract of DOI:10.1021/acs.orglett.8b01021

A protocol for the nickel-catalyzed alkylation of amides was established. The use of alkylboranes as nucleophilic partners allowed the use of mild reaction conditions and compatibility of various functional groups with respect to both coupling partners. The catalytic alkylation proceeded selectively at the amides in the presence of other functional groups as well as other carboxylic acid derived moieties.

Full text of DOI:10.1021/acs.orglett.8b01021

Letter
pubs.acs.org/OrgLett
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
Cross-Coupling of Amides with Alkylboranes via Nickel-Catalyzed
C−N Bond Cleavage
Xiangqian Liu,† Chien-Chi Hsiao,† Lin Guo,† and Magnus Rueping*,†,‡
†RWTH Aachen University, Institute of Organic Chemistry, Landoltweg 1, 52074 Aachen, Germany
‡King Abdullah University of Science and Technology (KAUST), Kaust Catalysis Center (KCC), Thuwal 23955-6900, Saudi Arabia
S
* Supporting Information
ABSTRACT: A protocol for the nickel-catalyzed alkylation of
amides was established. The use of alkylboranes as
nucleophilic partners allowed the use of mild reaction
conditions and compatibility of various functional groups
with respect to both coupling partners. The catalytic alkylation
proceeded selectively at the amides in the presence of other functional groups as well as other carboxylic acid derived moieties.
ver the past decades, transition-metal-catalyzed cross-
wildly used in the synthesis of complex natural products and the
Ocouplings have emerged as a powerful method for the development of modern drugs and organic materials.15,16
Among the alkylboron compounds commonly applied, B-
alkyl-9-BBNs, which can be readily prepared in situ by
hydroboration of the corresponding alkenes,17 have shown
high efficiency in couplings with a broad range of electrophilic
reagents.18,19 Inspired by these studies, we set forth to utilize B-
alkyl-9-BBNs as nucleophilic partners in the nickel-catalyzed
alkylation of amides. Although catalytic acyl Suzuki−Miyaura
reactions of acid halides,20 anhydrides,20a and activated
esters21,22 are known, the corresponding alkylation of amides
has not been established.
Herein, we describe a versatile nickel-catalyzed alkylative
Suzuki−Miyaura reaction of N-arylated amides via C−N bond
cleavage with high reactivity and broad functional group
tolerance with respect to both coupling partners (Scheme 1).
selective construction of carbon−carbon and carbon−heter-
oatom bonds both in the laboratory as well as on an industrial
scale.1 Although the developed transformations have often
involved catalysts based on palladium, good advances have been
achieved also in nickel catalysis.2 Nickel-catalyzed processes have
gained popularity mainly due to the key features of nickel, such as
facile oxidative addition3 and ready access to multiple oxidation
states,4 which have facilitated the development of a broad range
of innovative transformations.2 As such, nickel was successfully
applied in the activation of traditionally unreactive functional
groups including phenol derivatives,5 aromatic nitriles6 or
fluorides.7 In our continuous efforts to investigate and disclose
new reactivities based on nickel catalysis,8 we aimed to employ
amides, a typical stable functionality, as substrates in alkylation
reactions.
Amides are key building blocks of proteins and common
entities in natural and manufactured organic functional
molecules.9 In sharp contrast with their natural abundance,
methodologies to functionalize the amide group are limited due
to the resonance stability of the amide bond.9,10 Nevertheless, the
activation of amides11−13 was reported by the groups of Garg
(Ni)12a−c,e,f,h,i,n,v and Zou (Pd).13b,c In addition, the use of
twisted amides to destabilize the C−N bond was introduced by
the Szostak group (Ni, Pd, Rh).12,13 Many of the developed
transformations focus on the establishment of Cacyl−Caryl bonds,
complementing the Weinreb amide chemistry14 and allowing for
the synthesis of aryl ketones. In addition, Garg and co-workers
reported the nickel-catalyzed alkylation of Ts-activated amides
with alkylzinc reagents; however, N-Ph, Me amides were not
reactive under the developed conditions.12i Very recently, we
discovered that by applying different reaction conditions, aryl
phenyl esters could be selectively converted into alkylated arenes
or ketones.8j Hence, the development of general protocols for the
synthesis of alkyl ketones from amides is still highly desirable.
Because of their availability, broad functional group tolerance
as well as environmental friendliness, alkylboron compounds are
Scheme 1. Nickel-Catalyzed Alkylation of Amides with
Alkylboron Reagents
To reach our goal, we initially investigated the reactivity of amide
1a with B-alkyl-9-BBN 2a under nickel catalysis (Table 1).
Ligands play an essential role in the activation of inert bonds.
Hence, initially, the activity of various nickel complexes was
examined in the presence of Cs2CO3 in iPr2O at 90 °C.
Monodentate and bidentate phosphine ligands proved to be
inefficient in the transformation (Table 1, entries 1 and 2). To
our delight, when the N-heterocyclic carbene (NHC) ligand IPr·
Received: March 30, 2018
© XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.8b01021
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
a
a
Table 1. Optimization of the Reaction Conditions
Scheme 2. Substrate Scope of Amides
b
ligand
(mol %)
Ni(cod)2
(mol %)
yield
entry
base
solvent
(%)
1
2
3
PCy3 (10)
dcype (5)
5
5
5
Cs2CO3
Cs2CO3
Cs2CO3
iPr2O
iPr2O
iPr2O
SIPr·HCl
(10)
28
4
IPr·HCl (10)
IPr·HCl (20)
IPr·HCl (10)
IPr·HCl (10)
IPr·HCl (10)
IPr·HCl (10)
IPr·HCl (10)
IPr·HCl (10)
IPr·HCl (10)
IPr·HCl (10)
IPr·HCl (10)
IPr·HCl (10)
IPr·HCl (10)
IPr·HCl (10)
5
10
10
10
10
10
10
10
10
10
10
10
10
10
Cs2CO3
Cs2CO3
Cs2CO3
CsF
iPr2O
iPr2O
iPr2O
iPr2O
iPr2O
iPr2O
iPr2O
iPr2O
iPr2O
toluene
THF
48
60
61
23
34
44
72
5
6
7
8
Li2CO3
Na2CO3
K2CO3
KOtBu
K3PO4
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
9
10
11
12
13
14
15
38
56
43
34
85
68
Et2O
c
16
iPr2O
iPr2O
c,d
17
a
Reaction conditions: 1a (0.25 mmol), 2a (0.5 mmol), base (0.5
b
mmol), solvent (1.5 mL), sealed tube, 90 °C, 36 h. Yield of the
isolated product. LiCl (0.125 mmol) was added. 18 h.
c
d
a
Reaction conditions: 1 (0.25 mmol), 2a (0.5 mmol), Ni(cod)2 (0.025
mmol), IPr·HCl (0.025 mmol), K2CO3 (0.5 mmol), LiCl (0.0125
mmol), iPr2O (1.5 mL), sealed tube, 90 °C, 36 h. Reaction on a 1
mmol scale, 96 h.
HCl [1,3-bis(2,6-diisopropylphenyl)imidazolium chloride] was
tested, the desired cross-coupling product 3a was isolated in
moderate yield (Table 1, entry 4). Among the various N-Ph
amides evaluated, N-Ph, Me amide proved to be the most
reactive substrate (see Tables S1 and S3). Although the yield of
ketone 3a could be raised upon increasing the loading of
Ni(cod)2, the nickel to ligand ratio did not greatly influence the
transformation (Table 1, entries 5 and 6). A range of bases was
examined, and K2CO3 proved to be the most efficient for our
alkylation process (Table 1, entries 7−12). Furthermore, as
shown in Table 1, entries 13−15, the yield of ketone 3a dropped
remarkably when other solvents were used. In our previous work,
a Lewis acid could facilitate the cleavage of C−O bonds.8b Thus,
we questioned whether the C−N bond cleavage would proceed
more smoothly in the presence of a Lewis acid. To our delight,
after examining various Lewis acids (see Table S1), we could
isolate the corresponding ketone 3a in 85% yield when the
reaction was performed in the presence of 50 mol % of LiCl
(Table 1, entry 16). The yield dropped considerably when other
Ni sources were employed (see Table S1, entries 27−29) and
when the reaction time was shortened (Table 1, entry 17).
With the established reaction conditions in hand, we examined
the scope and compatibility of the amide substrates (Scheme 2).
Naphthyl, phenyl, and biphenyl derivatives 1a−c underwent the
transformation smoothly, providing the corresponding products
3a−c in high yields. Amide derivatives bearing electron-donating
methoxy (1d) or electron-withdrawing F (1e) and CF3 (1f)
groups showed similar reactivity, indicating that the electronic
nature of the substrate does not play an essential role in the cross-
coupling reaction. The alkylation also proceeded smoothly when
p- and m-methyl-substituted amides (1g and 1h) were used. The
b
methyl ketone derivative 1i, which was not tolerated in the
reaction with strong organometallic reagents, showed high
efficiency in the transformation. Furyl amide 1j was also
compatible with the transformation, and the desired product 3j
was isolated in excellent yield. However, other heterocyclic
derived substrates (e.g., pyridine and quinoline derived amides)
were not compatible with our reaction conditions.
To show the scalability of our transformation, the reaction
between 1a and 2a was performed on a 1 mmol scale, and the
corresponding product 3a was isolated in 73% yield after 96 h.
Furthermore, the generality of the alkylation was evaluated
with respect to a variety of B-alkyl-9-BBNs. As shown in Scheme
3, a range of alkylborane reagents with various functional groups
such as phenyl, p-methoxyphenyl, p-tolyl, p-fluorophenyl, and p-
trifluoromethyl phenyl were suitable for the alkylation
conditions, providing the corresponding products 3k−o in
good to high yields. Branched and long linear aliphatic boranes
were also compatible in the transformation, and the correspond-
ing ketones 3p and 3q were obtained in good yields. In addition,
a silyl ether and an ester derivative were also tested under our
conditions and yielded the desired products 3r and 3s with good
efficiency.
To demonstrate the utility of our protocol, two synthetic
applications were performed (Scheme 4). Exposing amide
derivative 4 to our coupling conditions, we obtained ketone 5
with high efficiency without affecting the methyl ester group.
When bisamide 6 was employed in the nickel-catalyzed
B
DOI: 10.1021/acs.orglett.8b01021
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
a
Scheme 3. Substrate Scope of B-Blkyl-9-BBNs
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.orglett.8b01021.
Detailed experimental procedures, spectral data for all
compounds, and 1H, 13C, and 19F NMR spectra (PDF)
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: magnus.rueping@rwth-aachen.de.
ORCID
Magnus Rueping: 0000-0003-4580-5227
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
X.L. and L.G. gratefully acknowledge financial support from the
China Scholarship Council. This research was supported by King
Abdullah University of Science and Technology (KAUST)
Office of Sponsored Research under Award No. URF/1/3030-
01.
REFERENCES
■
(1) (a) Handbook of Organopalladium Chemistry for Organic Synthesis;
Negishi, E.-i., Ed.; Wiley-Interscience: New York, 2002. (b) Metal-
Catalyzed Cross-Coupling Reactions; de Meijere, A., Diederich, F., Eds.;
Wiley-VCH: Weinheim, 2004. (c) Negishi, E. Angew. Chem., Int. Ed.
2011, 50, 6738. (d) Metal-Catalyzed Cross-Coupling Reactions and More;
a
Reaction conditions: 1a (0.25 mmol), 2 (0.5 mmol), Ni(cod)2 (0.025
mmol), IPr·HCl (0.025 mmol), K2CO3 (0.5 mmol), LiCl (0.0125
mmol), iPr2O (1.5 mL), sealed tube, 90 °C, 72 h. 2 (0.75 mmol) was
used.
de Meijere, A., Brase, S., Oestreich, M., Eds.; Wiley-VCH: Weinheim,
2014. (e) New Trends in Cross-Coupling: Theory and Applications;
Colacot, T., Ed.; RSC Catalysis Series: London, 2014.
̈
b
(2) For selected reviews, see: (a) Hu, X. Chem. Sci. 2011, 2, 1867.
(b) Jana, R.; Pathak, T. P.; Sigman, M. S. Chem. Rev. 2011, 111, 1417.
(c) Rosen, B. M.; Quasdorf, K. W.; Wilson, D. A.; Zhang, N.; Resmerita,
A.-M.; Garg, N. K.; Percec, V. Chem. Rev. 2011, 111, 1346. (d) Du, P.;
Eisenberg, R. Energy Environ. Sci. 2012, 5, 6012. (e) Han, F.-S. Chem. Soc.
Rev. 2013, 42, 5270. (f) Tasker, S. Z.; Standley, E. A.; Jamison, T. F.
Nature 2014, 509, 299. (g) Gui, Y.-Y.; Sun, L.; Lu, Z.-P.; Yu, D.-G. Org.
Chem. Front. 2016, 3, 522. (h) Ananikov, V. P. ACS Catal. 2015, 5, 1964.
(i) Ackermann, L. Chem. Commun. 2010, 46, 4866.
Scheme 4. Nickel-Catalyzed Chemoselective Alkylation of
Carboxylic Acid Derivatives
(3) Tsou, T. T.; Kochi, J. K. J. Am. Chem. Soc. 1979, 101, 6319.
(4) (a) Phapale, V. B.; Cardenas, D. J. Chem. Soc. Rev. 2009, 38, 1598.
(b) Breitenfeld, J.; Hu, X. Chimia 2014, 68, 235. (c) Cornella, J.; Gomez-
Bengoa, E.; Martin, R. J. Am. Chem. Soc. 2013, 135, 1997.
(5) (a) Tollefson, E. J.; Hanna, L. E.; Jarvo, E. R. Acc. Chem. Res. 2015,
48, 2344. (b) Tobisu, M.; Chatani, N. Acc. Chem. Res. 2015, 48, 1717.
(c) Cornella, J.; Zarate, C.; Martin, R. Chem. Soc. Rev. 2014, 43, 8081.
(d) Yamaguchi, J.; Muto, K.; Itami, K. Eur. J. Org. Chem. 2013, 2013, 19.
(e) Mesganaw, T.; Garg, N. K. Org. Process Res. Dev. 2013, 17, 29. (f) Yu,
D. G.; Li, B. J.; Shi, Z. J. Acc. Chem. Res. 2010, 43, 1486.
alkylation, the N-alkyl, alkyl amide group survived and the
corresponding product 7 was isolated in 69% yield. By applying
the orthogonal reactivity between different carboxylic acid
derived groups, the alkylation proceeded chemoselectively.
In summary, we have developed a versatile nickel-catalyzed
alkylation of amides with alkylboranes as nucleophilic counter-
parts. The N-Ph, Me amides were cleaved under mild conditions
and coupled with a range of functionalized alkylboranes with high
efficiency. The catalytic alkylation proceeded selectively at the
C−N bond of N-Ph, Me amides in the presence of ester and N-
alkyl, alkyl amide groups. The good chemoselectivity exhibited
by our protocol may not be achieved by applying the traditional
ketone synthesis from amides in which typically strong
organometallic reagents have to be used.
(6) Bonesi, S. M.; Fagnoni, M. Chem. - Eur. J. 2010, 16, 13572.
(7) Amii, H.; Uneyama, K. Chem. Rev. 2009, 109, 2119.
(8) Selected articles from our group: (a) Leiendecker, M.; Hsiao, C. C.;
Guo, L.; Alandini, N.; Rueping, M. Angew. Chem., Int. Ed. 2014, 53,
12912. (b) Liu, X.; Hsiao, C. C.; Kalvet, I.; Leiendecker, M.; Guo, L.;
Schoenebeck, F.; Rueping, M. Angew. Chem., Int. Ed. 2016, 55, 6093.
(c) Guo, L.; Hsiao, C.-C.; Yue, H.; Liu, X.; Rueping, M. ACS Catal. 2016,
6, 4438. (d) Guo, L.; Chatupheeraphat, A.; Rueping, M. Angew. Chem.,
Int. Ed. 2016, 55, 11810. (e) Guo, L.; Liu, X.; Baumann, C.; Rueping, M.
Angew. Chem., Int. Ed. 2016, 55, 15415. (f) Yue, H.; Guo, L.; Liu, X.;
Rueping, M. Org. Lett. 2017, 19, 1788. (g) Liu, X.; Jia, J.; Rueping, M.
ACS Catal. 2017, 7, 4491. (h) Yue, H.; Zhu, C.; Rueping, M. Org. Lett.
2018, 20, 385. (i) Yue, H.; Zhu, C.; Rueping, M. Angew. Chem., Int. Ed.
2018, 57, 1371. (j) Chatupheeraphat, A.; Liao, H.-H.; Srimontree, W.;
C
DOI: 10.1021/acs.orglett.8b01021
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Guo, L.; Minenkov, Y.; Poater, A.; Cavallo, L.; Rueping, M. J. Am. Chem.
Soc. 2018, 140, 3724.
(9) The Amide Linkage: Structural Significance in Chemistry,
Biochemistry, and Materials Science; Greenberg, A., Breneman, C. M.,
Liebman, J. F., Eds.; Wiley: New York, 2003.
(10) (a) Pauling, L.; Corey, R. B.; Branson, H. R. Proc. Natl. Acad. Sci.
U. S. A. 1951, 37, 205. (b) The Nature of the Chemical Bond; Pauling, L.,
Ed.; Cornell University Press: Ithaca, 1960.
(11) (a) Meng, G.; Shi, S.; Szostak, M. Synlett 2016, 27, 2530.
(b) Dander, J. E.; Garg, N. K. ACS Catal. 2017, 7, 1413. (c) Liu, C.;
Szostak, M. Chem. - Eur. J. 2017, 23, 7157. (d) Gao, Y.; Ji, C.-L.; Hong, X.
Sci. China: Chem. 2017, 60, 1413. (e) Takise, R.; Muto, K.; Yamaguchi, J.
Chem. Soc. Rev. 2017, 46, 5864.
additions: (q) Yada, A.; Okajima, S.; Murakami, M. J. Am. Chem. Soc.
2015, 137, 8708. (r) Meng, G.; Szostak, M. Angew. Chem., Int. Ed. 2015,
54, 14518. (s) Liu, C.; Meng, G.; Szostak, M. J. Org. Chem. 2016, 81,
12023. Pd-catalyzed Transamidation: (t) Meng, G.; Lei, P.; Szostak, M.
Org. Lett. 2017, 19, 2158. Rhodium-catalyzed arylations: (u) Meng, G.;
Szostak, M. Org. Lett. 2016, 18, 796. (v) Wu, H.; Liu, T.; Cui, M.; Li, Y.;
Jian, J.; Wang, H.; Zeng, Z. Org. Biomol. Chem. 2017, 15, 536. (w) Meng,
G.; Szostak, M. ACS Catal. 2017, 7, 7251. Pd-catalyzed cyanation:
(x) Shi, S.; Szostak, M. Org. Lett. 2017, 19, 3095. Co-catalyzed
esterification (y) Bourne-Branchu, Y.; Gosmini, C.; Danoun, G. Chem. -
Eur. J. 2017, 23, 10043.
(14) Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815.
(15) For a review on the total synthesis with alkylboron reagents, see:
Chemler, S. R.; Trauner, D.; Danishefsky, S. Angew. Chem., Int. Ed. 2001,
40, 4544.
(16) Selected examples: (a) Yuan, Y.; Men, H.; Lee, C. J. Am. Chem.
Soc. 2004, 126, 14720. (b) Tsukano, C.; Ebine, M.; Sasaki, M. J. Am.
Chem. Soc. 2005, 127, 4326. (c) Smith, A. B., III; Davulcu, A. H.; Kurti, L.
Org. Lett. 2006, 8, 1665. (d) Roulland, E. Angew. Chem., Int. Ed. 2008, 47,
3762. (e) Williams, D. R.; Walsh, M. J.; Miller, N. A. J. Am. Chem. Soc.
2009, 131, 9038.
(17) (a) Organic Syntheses via Boranes; Brown, H. C., Ed.; Wiley: New
York, 1975. (b) Soderquist, J. A.; Justo de Pomar, J. C. Tetrahedron Lett.
2000, 41, 3537. (c) Saito, B.; Fu, G. C. J. Am. Chem. Soc. 2007, 129, 9602.
(18) Selected Csp2−Csp3 Suzuki−Miyaura couplings: (a) Miyaura, N.;
Ishiyama, T.; Sasaki, H.; Ishikawa, M.; Sato, M.; Suzuki, A. J. Am. Chem.
Soc. 1989, 111, 314. (b) Campbell, A. D.; Raynham, T. M.; Taylor, R. J.
K. Tetrahedron Lett. 1999, 40, 5263. (c) Kamatani, A.; Overman, L. E. J.
Org. Chem. 1999, 64, 8743. (d) Sabat, M.; Johnson, C. R. Org. Lett. 2000,
2, 1089. (e) Vice, S.; Bara, T.; Bauer, A.; Evans, C. A.; Ford, J.; Josien, H.;
McCombie, S.; Miller, M.; Nazareno, D.; Palani, A.; Tagat, J. J. Org.
Chem. 2001, 66, 2487. (f) Potuzak, J. S.; Tan, D. S. Tetrahedron Lett.
2004, 45, 1797. (g) Walker, S. D.; Barder, T. E.; Martinelli, J. R.;
Buchwald, S. L. Angew. Chem., Int. Ed. 2004, 43, 1871. (h) Zheng, W.;
DeMattei, J. A.; Wu, J.-P.; Duan, J. J. W.; Cook, L. R.; Oinuma, H.; Kishi,
Y. J. Am. Chem. Soc. 1996, 118, 7946. (i) Narukawa, Y.; Nishi, K.; Onoue,
H. Tetrahedron 1997, 53, 539.
(12) For Ni-catalyzed transformations of amides, see: Esterification:
(a) Hie, L.; Fine Nathel, N. F.; Shah, T. K.; Baker, E. L.; Hong, X.; Yang,
Y. F.; Liu, P.; Houk, K. N.; Garg, N. K. Nature 2015, 524, 79. (b) Hie, L.;
Baker, E. L.; Anthony, S. M.; Desrosiers, J. N.; Senanayake, C.; Garg, N.
K. Angew. Chem., Int. Ed. 2016, 55, 15129. (c) Dander, J. E.; Weires, N.
A.; Garg, N. K. Org. Lett. 2016, 18, 3934. (d) Deguchi, T.; Xin, H.-L.;
Morimoto, H.; Ohshima, T. ACS Catal. 2017, 7, 3157. Transamidation:
(e) Baker, E. L.; Yamano, M. M.; Zhou, Y.; Anthony, S. M.; Garg, N. K.
Nat. Commun. 2016, 7, 11554. (f) Dander, J. E.; Baker, E. L.; Garg, N. K.
Chem. Sci. 2017, 8, 6433. (g) Cheung, C. W.; Ploeger, M. L.; Hu, X. ACS
Catal. 2017, 7, 7092. Ketone formation: (h) Weires, N. A.; Baker, E. L.;
Garg, N. K. Nat. Chem. 2016, 8, 75. (i) Simmons, B. J.; Weires, N. A.;
Dander, J. E.; Garg, N. K. ACS Catal. 2016, 6, 3176. (j) Shi, S.; Szostak,
M. Chem. - Eur. J. 2016, 22, 10420. (k) Shi, S.; Szostak, M. Org. Lett.
2016, 18, 5872. (l) Ni, S.; Zhang, W.; Mei, H.; Han, J.; Pan, Y. Org. Lett.
2017, 19, 2536. (m) Walker, J. A.; Vickerman, K. L.; Humke, J. N.;
Stanley, L. M. J. Am. Chem. Soc. 2017, 139, 10228. (n) Medina, J. M.;
Moreno, J.; Racine, S.; Du, S.; Garg, N. K. Angew. Chem., Int. Ed. 2017,
56, 6567. (o) Boit, T. B.; Weires, N. A.; Kim, J.; Garg, N. K. ACS Catal.
2018, 8, 1003. Arylation, borylation, and amination: (p) Shi, S.; Meng,
G.; Szostak, M. Angew. Chem., Int. Ed. 2016, 55, 6959. (q) Hu, J.; Zhao,
Y.; Liu, J.; Zhang, Y.; Shi, Z. Angew. Chem., Int. Ed. 2016, 55, 8718.
(r) Yue, H.; Guo, L.; Liao, H.-H.; Cai, Y.; Zhu, C.; Rueping, M. Angew.
Chem., Int. Ed. 2017, 56, 4282. (s) Liu, X.; Yue, H.; Jia, J.; Guo, L.;
Rueping, M. Chem. - Eur. J. 2017, 23, 11771. (t) Lee, S.-C.; Guo, L.; Yue,
H.; Liao, H.-H.; Rueping, M. Synlett 2017, 28, 2594. Reductive
reactions: (u) Dey, A.; Sasmal, S.; Seth, K.; Lahiri, G. K.; Maiti, D. ACS
Catal. 2017, 7, 433. (v) Yue, H.; Guo, L.; Lee, S.-C.; Liu, X.; Rueping, M.
Angew. Chem., Int. Ed. 2017, 56, 3972. (w) Simmons, B. J.; Hoffmann,
M.; Hwang, J.; Jackl, M. K.; Garg, N. K. Org. Lett. 2017, 19, 1910. Retro-
hydroamidocarbonylation: (x) Hu, J.; Wang, M.; Pu, X.; Shi, Z. Nat.
Commun. 2017, 8, 14993. Alkynylation: (y) Srimontree, W.;
Chatupheeraphat, A.; Liao, H.-H.; Rueping, M. Org. Lett. 2017, 19,
3091. Cyanation: (z) Chatupheeraphat, A.; Liao, H.-H.; Lee, S.-C.;
Rueping, M. Org. Lett. 2017, 19, 4255. Thioetherification: (aa) Lee, S.-
C.; Liao, H.-H.; Chatupheeraphat, A.; Rueping, M. Chem. - Eur. J. 2018,
24, 3608.
(13) For further selected examples of metal-catalyzed cross-coupling
reactions with amides, see: Pd-catalyzed ketone formation: (a) Meng,
G.; Szostak, M. Org. Lett. 2015, 17, 4364. (b) Li, X.; Zou, G. Chem.
Commun. 2015, 51, 5089. (c) Li, X.; Zou, G. J. Organomet. Chem. 2015,
794, 136. (d) Meng, G.; Szostak, M. Org. Biomol. Chem. 2016, 14, 5690.
(e) Liu, C.; Meng, G.; Liu, Y.; Liu, R.; Lalancette, R.; Szostak, R.;
Szostak, M. Org. Lett. 2016, 18, 4194. (f) Meng, G.; Shi, S.; Szostak, M.
ACS Catal. 2016, 6, 7335. (g) Wu, H.; Cui, M.; Jian, J.; Zeng, Z. Adv.
Synth. Catal. 2016, 358, 3876. (h) Cui, M.; Wu, H.; Jian, J.; Wang, H.;
Liu, C.; Daniel, S.; Zeng, Z. Chem. Commun. 2016, 52, 12076. (i) Lei, P.;
Meng, G.; Szostak, M. ACS Catal. 2017, 7, 1960. (j) Liu, C.; Liu, Y.; Liu,
R.; Lalancette, R.; Szostak, R.; Szostak, M. Org. Lett. 2017, 19, 1434.
(k) Shi, S.; Lei, P.; Szostak, M. Organometallics 2017, 36, 3784. (l) Meng,
G.; Szostak, R.; Szostak, M. Org. Lett. 2017, 19, 3596. (m) Lei, P.; Meng,
G.; Ling, Y.; An, J.; Szostak, M. J. Org. Chem. 2017, 82, 6638. (n) Lei, P.;
Meng, G.; Shi, S.; Ling, Y.; An, J.; Szostak, R.; Szostak, M. Chem. Sci.
2017, 8, 6525. (o) Lei, P.; Meng, G.; Ling, Y.; An, J.; Nolan, S. P.;
Szostak, M. Org. Lett. 2017, 19, 6510. (p) Meng, G.; Lalancette, R.;
Szostak, R.; Szostak, M. Org. Lett. 2017, 19, 4656. Pd-catalyzed olefin
(19) Selected Csp3−Csp3 Suzuki−Miyaura couplings: (a) Ishiyama, T.;
Abe, S.; Miyaura, N.; Suzuki, A. Chem. Lett. 1992, 21, 691. (b) Netherton,
M. R.; Dai, C.; Neuschutz, K.; Fu, G. C. J. Am. Chem. Soc. 2001, 123,
̈
10099. (c) Kirchhoff, J. H.; Dai, C.; Fu, G. C. Angew. Chem., Int. Ed.
2002, 41, 1945. (d) Arentsen, K.; Caddick, S.; Cloke, F. G. N.; Herring,
A. P.; Hitchcock, P. B. Tetrahedron Lett. 2004, 45, 3511. (e) Brenstrum,
T.; Gerristma, D. A.; Adjabeng, G. M.; Frampton, C. S.; Britten, J.;
Robertson, A. J.; McNulty, J.; Capretta, A. J. Org. Chem. 2004, 69, 7635.
(f) Valente, C.; Baglione, S.; Candito, D.; O’Brien, C. J.; Organ, M. G.
Chem. Commun. 2008, 735. (g) Achonduh, G. T.; Hadei, N.; Valente, C.;
Avola, S.; O’Brien, C. J.; Organ, M. G. Chem. Commun. 2010, 46, 4109.
(h) Lu, Z.; Fu, G. C. Angew. Chem., Int. Ed. 2010, 49, 6676.
(20) (a) Blangetti, M.; Rosso, H.; Prandi, C.; Deagostino, A.;
Venturello, P. Molecules 2013, 18, 1188. (b) Kabalka, G. W.; Malladi,
R. R.; Tejedor, D.; Kelley, S. Tetrahedron Lett. 2000, 41, 999. (c) Yasui,
Y.; Tsuchida, S.; Miyabe, H.; Takemoto, Y. J. Org. Chem. 2007, 72, 5898.
(21) (a) Tatamidani, H.; Kakiuchi, F.; Chatani, N. Org. Lett. 2004, 6,
3597. (b) Tatamidani, H.; Yokota, K.; Kakiuchi, F.; Chatani, N. J. Org.
Chem. 2004, 69, 5615. (c) Yu, Y.; Liebeskind, L. S. J. Org. Chem. 2004,
69, 3554. (d) Isshiki, R.; Takise, R.; Itami, K.; Muto, K.; Yamaguchi, J.
Synlett 2017, 28, 2599. (e) Ben Halima, T.; Zhang, W.; Yalaoui, I.; Hong,
X.; Yang, Y.-F.; Houk, K. N.; Newman, S. G. J. Am. Chem. Soc. 2017, 139,
1311.
(22) For an alternative Ni-catalyzed protocol for the synthesis of
ketones, see: Vandavasi, J. K.; Hua, X. Y.; Halima, H. B.; Newman, S. G.
Angew. Chem., Int. Ed. 2017, 56, 15441.
D
DOI: 10.1021/acs.orglett.8b01021
Org. Lett. XXXX, XXX, XXX−XXX