Cobalt(III)-Catalyzed Alkylation of Primary C(sp3)–H Bonds with Diazo Compounds

Article abstract of DOI:10.1002/adsc.201700636

Chelation-assisted C(sp²)–H metalation/carbenoid insertion has been well investigated. However, the analogous carbene functionalization of C(sp³)–H bonds remains a great challenge. Here we report the first cobalt(III)-catalyzed alkyl

Full text of DOI:10.1002/adsc.201700636

Title: Cobalt(III)-Catalyzed Alkylation of Primary C(sp3)-H Bonds with
Diazo Compounds
Authors: Sheng-Yi Yan, Peng-Xiang Ling, and Bing-Feng Shi
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10.1002/adsc.201700636
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Cobalt(III)-Catalyzed Alkylation of Primary C(sp3)-H Bonds
with Diazo Compounds
Sheng-Yi Yan,a Peng-Xiang Ling,a,b and Bing-Feng Shi*a
a
Department of Chemistry, Zhejiang University, Hangzhou 310027, China
Fax: (+86)-571-8795-1895, phone: (+86)-571-8898-1229, e-mail: bfshi@zju.edu.cn
School of Chemical & Environmental Engineering, Wuyi University, Jiangmen, 529020, China
b
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Rh(III) catalyst.[5] Since then, chelation-assisted
Abstract.
Chelation-assisted
C(sp2)–H
metalation/carbenoid insertion has been well investigated. metal-catalyzed carbene migratory insertion into
C(sp2)-H bonds has been thoroughly studied by
However, the analogous carbene functionalization of
C(sp3)–H bonds remains a great challenge. Here we report
Rovis, Li, Glorius, Wang, Ackermann and many
others.[6-8] Despite these elegant progress, this
the first Cobalt(III)-catalyzed alkylation of 8-
methylquinolines with diazo compounds through primary
C(sp3)–H cobaltation/carbenoid insertion. The reaction is
highly efficient, scalable and tolerates a variety of
functional groups. Furthermore, the unique protocol can be
applied to the synthesis of azatricyclic antibiotic
compounds.
novel reaction protocol is limited to the migratory
insertion of diazo compounds into aromatic or
alkenyl C(sp2)–H bonds and only one example of
Rh(III)-catalyzed carbene insertion into non-
acidic primary C(sp3)-H bonds has been realized
by Zhou recently.[9] In this respect, novel designs
and the development of a complementary reaction
to enable the selective carbene functionalization
of primary C(sp3)–H bonds, which overwhelms
the inherent selectivity of classic metal-carbene
insertion and C–H metalation/carbene migratory
insertion, would be highly desirable, yet
challenging.
Keywords: cobalt; carbenoid insertion; alkylation; C(sp3)–
H activation; diazo compounds
Over the past decade, metal-carbene insertion
into aliphatic C-H bonds has emerged as a
powerful strategy to construct C-C bonds.[1] The
classic metal-carbene insertion proceeds with a
concerted reaction mechanism and exhibits high
levels of selectivity controlled by electronic
effects, showing an order of activation of tertiary
> secondary >> primary C(sp3)–H. Although
significant progress has been achieved on the
insertion into tertiary and secondary C(sp3)–H,
the analogous carbene functionalization of
primary C(sp3)–H bonds remains
a
great
challenge.[2]
Recently, the pioneering work by Wang, Satoh,
and Miura on metal-catalyzed C-H alkylation of
1,3-azoles with N-tosylhydrazones demonstrated
that an alternative new reaction pattern was also
operative.[3] In contrast to the classic concerted
metal-carbene insertion, this novel process is
believed to follow a pathway involving C–H
metalation, metal-carbene formation, and
subsequent migratory insertion.[4] Shortly after, a
significant breakthrough was made by Yu and co-
workers, who elegantly reported the first example
of chelation-assisted insertion of aromatic
C(sp2)–H bonds into α-diazomalonates using a
Scheme 1. Cp*Co(III)-Catalyzed C–H Functionalization
with Diazo Compounds.
1
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10.1002/adsc.201700636
Advanced Synthesis & Catalysis
More recently, the use of earth-abundant first- desired product 3a was afforded in 10% yield
row transition metal catalysts, such as cobalt, has
(Table 1, entry 1). A survey of different solvents
received tremendous attention.[10] In particular, led us to identify that dichloromethane (DCM)
since the pioneering work of Kanai and was the best reaction medium and the yield was
Matsunaga,[11] high-valent Cp*Co(III) (Cp* = increased to 37% (entries 2–4). Mn(OAc)2 was
pentamethylcyclopentadienyl)
has
been found to be effective for the transformation,
recognized as a robust and versatile catalyst due giving 3a in 45% yield (entry 5). When the
to its excellent reactivity.[12] However, so far, amount of Mn(OAc)2 was increased to 1.0
only a few examples of Co(III)-catalyzed carbene equivalent, the desired product 3a was obtained
migratory insertion into C(sp2)−H bonds have in 78% yield (entry 6). To our delight, when
been reported. In 2015, Wang reported
AgOAc was removed, the yield was further
Cp*Co(III)-catalyzed alkylation of (hetero)arenes increased (entry 7, 89%). Finally, control
with α-diazomalonates (Scheme 1a).[8a] Glorius experiment suggested that no desired product was
realized the first example of Cp*Co(III)- observed when the reaction was conducted in the
catalyzed C–H coupling with diazo compounds to
construct conjugated polycyclic hydrocarbons
with tunable emission wavelengths (Scheme
1b).[8b] Later, Glorius and Ackermann reported
Co(III)-catalyzed synthesis of isoquinoline
derivatives with diazo compounds using imine as
directing group, respectively (Scheme 1b).[8c,8d]
Inspired by these reports and as a continuation of
our interest in Cp*Co(III)-catalyzed C-H
functionalization,[13] here we disclose the first
Co(III)-catalyzed alkylation of primary C(sp3)−H
bonds with diazo compounds (Scheme 1c).
Mechanistically, this protocol proceeds through a
quinolyl-directed C(sp3)–H cobaltation, Co-
carbene formation, migratory insertion and
subsequent protonation. The reaction is scalable
and has been successfully applied to the synthesis
of azatricyclic antibiotic compounds.
absence of Cp*Co(CO)I2.
Table 2. The substrate scope of 8-methylquinoline.[a]
Table 1. Optimization of the reaction conditions.[a]
AgOAc
(mol%)
20
Yield
(%)[b]
10
37
0
Entry
Additive (equiv) Solvent
1
2
3
NaOAc (0.2)
NaOAc (0.2)
NaOAc (0.2)
NaOAc (0.2)
DCE
DCM
MeCN
TFE
20
20
20
4
0
5
6
20
20
0
0
Mn(OAc)2 (0.2) DCM
Mn(OAc)2 (1.0) DCM
Mn(OAc)2 (1.0) DCM
Mn(OAc)2 (1.0) DCM
45
78
7
89[c]
0
8[d]
[a] Reaction conditions: 1a (0.1 mmol), 2a (0.12 mmol),
[a] Reaction conditions: 1 (0.1 mmol), 2a (0.12 mmol),
Cp*Co(CO)I2 (10 mol%), AgSbF6 (20 mol%), solvent (1
o
1
Cp*Co(CO)I2 (10 mol%), AgSbF6 (20 mol%), Mn(OAc)2
mL), Ar, 120 C, 12 h. [b] Yield were determined by H
NMR using CH2Br2 as internal standard. [c] Isolated yield.
[d] No Cp*Co(CO)I2.
o
(1.0 equiv), DCM (1 mL) under Ar at 120 C for 12 h.
isolated yield.
With the optimal reaction conditions in hand,
we next investigated the substrate scope of
substituted 8-methyl quinolines (Table 2). In
general, diverse substituents at the C-5 position
To begin, we chose 8-methylquinoline (1a) as
model substrate,[14] and diethyl diazomalonate 2a
as coupling partner in the presence of 10 mol% of
Cp*Co(CO)I2 as catalyst and catalytic amounts of
AgSbF6, AgOAc and NaOAc as additives in 1,2-
were tolerated with the reaction conditions (3b
-
o
3p). In particular, halides, such as fluoride,
dichloroethane at 120 C for 12 h, and the
2
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10.1002/adsc.201700636
Advanced Synthesis & Catalysis
chloride, bromide, and iodide, were all
compatible with this protocol, giving the
alkylated products in good yields (3b-3e, 60%-
Scheme 2. Gram-scale synthesis and derivatization of
3a.
67%). The strong electron-withdrawing nitro
group was also feasible, albeit giving the product
To demonstrate the synthetic utility of this
in a reduced yield (3h, 21%). The amine group protocol, a scale-up reaction (5 mmol) has been
bearing free hydrogen atom was also tolerated,
giving 3i in 30% yield. Furthermore, the carbene
migratory insertion occurred smoothly in the
presence of alkenyl and alkynyl substituents on
conducted at a reduced catalyst loading (5 mol%
Cp*Co(CO)I2), and the alkylated product 3a was
obtained in 82% yield (Scheme 2, 1.24 g). 3a
could be transformed to ethyl 3-oxo-1,2,3,5,6,7-
hexahydropyrido[3,2,1-ij]quinoline-2-carboxylate
the backbone of the arene (3l-3o, 79%-90%
5
in 52% yield in the presence of
yield). To our delight, Bpin group at C-5 position
of quinoline, was also survived, affording the
desired product 3p in 87% yield; this was a
synthetically important result as such substituent
could serve as a versatile handle for cross-
coupling reaction. Substituents at C-6 or the
sterically hindered C-7 position of the quinoline
also reacted smoothly with diethyl diazomalonate
NaBH(CN)3/BF3·Et2O.
Moreover, the synthetic potential of this
protocol was demonstrated by the elaboration of
alkylated product 3a to the important
intermediate of azatricyclic antibiotic compounds
(Scheme 3).[16] Reducing of 3a with LiAlH4,
followed by protection of the corresponding diol
with
compound
oxide in 64% yield with m-CPBA. After
2,2-dimethoxypropane,
could
give
2a (3q-3u).
6
, which could be oxidized to the N-
7
introduction of methoxyl group at the C-2
position and subsequent removal of the
Table 3. The scope of diazo compounds.
isoproylidene group, diol
could be further elaborated to azatricyclic
antibiotic compounds.
9 was affored. The diol
9
Scheme 3. Synthesis the intermediate of azatricyclic
antibiotic compounds. Reagents and conditions: a)
LiAlH4, THF, 6 h, 61%; b) 2,2-dimethoxypropane,
TsOH, acetone, rt, 3 h, 93%; c) m-CPBA, CHCl3, rt,
overnight, 64%; d) benzoyl chloride, NaOH (aq),
CH2Cl2, 0 oC, 1 h; e) MeI, DMF, K2CO3, 100 oC, 10 h,
47% for two steps; f) TFA/H2O (1:1), rt, overnight,
85%.
Next, we explored the reactivity of various
carbene precursors with 8-methylquinoline 1a
(Table 3). Both the symmetrical and
unsymmetrical diazomalonates (4a–4e) were
compatible with the reaction. However, the
coupling of 1a with di-tert-butyl diazomalonate
2c only gave the alkylated product 4c in 28%
yield.
When
ethyl
2-diazo-2-
(phenylsulfonyl)acetate 2f was used as carbene
precursor, the alkylation product was obtained in
excellent yield (4f, 90%). It’s structure was
In order to gain some insights into the
mechanism of this reaction,
a
series of
unambiguously
confirmed
by
X-
crystallography.[15] Unfortunately, other α-
diazocarbonyl compounds obtained from β-keto
ester, β-diketo, α-aryl ester compounds failed to
produce any desired product.
experiments have been performed. First, the
reversibility of the C-H activation step was
studied. A significant H/D exchange was
observed when [D3]-1a was subjected to the
standard conditions in the absence of carbene
precursor 2a (Scheme 4a). However, essentially
no H/D exchange was detected in the recovered
starting material 1a in the presence of 2a
(Scheme 4b). These results suggested that the
carbene formation/migratory insertion process
was significantly faster than the back reaction of
3
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10.1002/adsc.201700636
Advanced Synthesis & Catalysis
the C–H activation step. Second, the kinetic
isotope effect was investigated in parallel and
competition experiments (Scheme 4c). A PH/PD
value of 6.7 (parallel experiment) and 8.1
(competition experiment) were observed. These
rather large values of PH/PD indicate that cleavage
of the C-H bond is likely involved in the rate-
determining step.[17] Finally, we investigate
whether the reaction mechanism could proceed in
a classic concerted metal-carbene insertion or
quinolyl-assisted
primary
C(sp3)-H
activation/carbenoid insertion. As shown in
Scheme 4d, when 8-ethylquinoline (10a) and 8-
isopropylquinoline (10b) were subjected to the
standard reaction conditions respectively, no
alkylated product was observed. The reaction
tendency is in accordance with the quinolyl-
assisted primary C(sp3)-H activation/carbenoid
insertion pathway.
Figure 1. Plausible catalytic cycle.
In summary, we have developed for the first
time an efficient Cp*Co(III)-catalyzed coupling
8-methylquinoline with diazo compounds via
C(sp3)−H bond activation process. The protocol
tolerates a variety of functional group and can be
scaled up easily. A plausible reaction mechanism
has been proposed, moreover the alkylated
products can be derived to synthesize important
intermediate
of
azatricyclic
antibiotic
compounds. Further studies aimed at applying
this catalytic system to other more challenging
C(sp3)−H bond are underway in our laboratory.
Experimental Section
General Procedure for the Alkylation of 8-
Methylquinolines with Diazo Compounds. To a 50 mL
Schlenk tube was added 8-aminoquinoline 1 (0.1 mmol),
diazo compound 2 (0.12 mmol), Mn(OAc)2 (17.3 mg, 0.1
mmol), Cp*Co(CO)I2 (4.8 mg, 0.01 mmol), then AgSbF6
(6.9 mg, 0.02 mmol) and DCM (1 mL). The vial was
evacuated and filled with Ar (1 atm) and then stirred at
120 °C for 12 h. After cooling to room temperature, the
mixture was diluted with ethyl acetate, filtrated through
ceilt. After concentration, the resulting residue was
purified by preparative TLC using hexane/EtOAc as the
eluent to afford the product.
Scheme 4. Mechanistic studies.
Based on the preliminary experimental results
and literature precedents,[4-8] we proposed a
plausible mechanism in Figure 1. The active
catalyst Cp*CoIII
I is generated by the ligand
abstraction with AgSbF6. Cobaltacycle II was
formed by a rating-determining C-H bond
cleavage process. Cobaltacycle II may further
react with the diazo compound to form the metal–
carbene intermediate III by dediazonization.
Subsequently, cobalt-carbene migratory insertion
affords intermediate IV, followed by protonation
with the HOAc to afford the alkylated product
Acknowledgements
Financial support from the NSFC (21422206, 21572201),
the National Basic Research Program of China
(2015CB856600) and Zhejiang Provincial NSFC
(LR17B020001) is gratefully acknowledged.
and regenerates the active catalyst species I.
References
[1] For recent reviews, see: a) H. M. L. Davies, D.
Morton, Chem. Soc. Rev. 2011, 40, 1857; b) M. P.
Doyle, R. Duffy, M. Ratnikov, L. Zhou, Chem. Rev.
2010, 110, 704; b) H. M. L. Davies, J. R. Manning,
Nature 2008, 451, 417.
4
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10.1002/adsc.201700636
Advanced Synthesis & Catalysis
[2] For examples on steric-effect controlled site-
selectivity using sterically more demanding rhodium
catalysts, see: a) C. M. Qin, H. M. Davies, J. Am.
Chem. Soc. 2014, 136, 9792; b) D. M. Guptill, H. M.
L. Davies, J. Am. Chem. Soc. 2014, 136, 17718.
Q.-J. Li, Z.-S. Huang, D. Li, H.-G. Wang, Chem.
Commun. 2015, 51, 10240.
[8] For examples catalyzed by Co(III), see: a) X.-G. Liu,
S.-S. Zhang, J.-Q. Wu, Q. Li, H. Wang, Tetrahedron
Lett. 2015, 56, 4093; b) D. Zhao, J. H. Kim, L.
Stegemann, C. A. Strassert, F. Glorius, Angew. Chem.
Int. Ed. 2015, 54, 4508; c) J. Li, M.-Y. Tang, L. Zang,
X.-L. Zhang, Z. Zhang, L. Ackermann, Org. Lett.
2016, 18, 2742; d) J. H. Kim, S. Greβies, F. Glorius,
Angew. Chem. Int. Ed. 2016, 55, 5577.
[3] a) X. Zhao, G. Wu, Y. Zhang, J. Wang, J. Am. Chem.
Soc. 2011, 133, 3296; b) T. Yao, K. Hirano, T. Satoh,
M. Miura, Angew. Chem. Int. Ed. 2012, 51, 775.
[4] For reviews, see: a) Q. Xiao, Y. Zhang, J. Wang, Acc.
Chem. Res. 2013, 46, 236; b) Z. Liu, J. Wang, J. Org.
Chem. 2013, 78, 10024; c) Y. Xia, Y. Zhang, J. Wang, [9] W. Hou, Y.-X. Yang, Y.-X. Wang, H.-J. Fang, Y.-C.
ACS Catal. 2013, 3, 2586; d) F. Hu, Y. Xia, C. Ma, Y.
Zhang, J. Wang, Chem. Commun. 2015, 51, 7986; e)
M. Peña-López, M. Beller, Angew. Chem. Int. Ed.
2017, 56, 46.
Li, B. Zhou, Chem. Commun. 2016, 52, 9672.
[10] For recent reviews, see: a) S. I. Kozhushkov, H. K.
Potukuchi, L. Ackermann, Catal. Sci. Technol. 2013,
3, 562; b) K. Gao, N. Yoshikai, Acc. Chem. Res. 2014,
47, 1208; c) L. Ackermann, J. Org. Chem. 2014, 79,
8948; d) N. Yoshikai, ChemCatChem 2015, 7, 732; e)
M. Moselage, J. Li, L. Ackermann, ACS Catal. 2016,
6, 498; f) D. Wei, X. Zhu, J.-L. Niu, M.-P. Song,
ChemCatChem. 2016, 8, 1242.
[5] W.-W. Chan, S.-F. Lo, Z. Zhou, W.-Y. Yu, J. Am.
Chem. Soc. 2012, 134, 13565.
[6] For selected representative examples catalyzed by
Rh(III), see: a) T. K. Hyster, K. E. Ruhl, T. Rovis, J.
Am. Chem. Soc. 2013, 135, 5364; b) Z. Shi, D. C.
Koester, M. Boultadakis- Arapinis, F. Glorius, J. Am.
Chem. Soc. 2013, 135, 12204; c) X.-Z. Yu, S.-J. Yu, J.
Xiao, B.-S. Wan, X.-W. Li, J. Org. Chem. 2013, 78,
5444; d) S. Cui, Y. Zhang, D. Wang, Q. Wu, Chem.
Sci. 2013, 4, 3912; e) F.-D. Hu, Y. Xia, F. Ye, Z.-X.
Liu, C. Ma, Y. Zhang, J.-B. Wang, Angew. Chem., Int.
Ed. 2014, 53, 1364; f) J. Jeong, P. Patel, H. Hwang, S.
Chang, Org. Lett. 2014, 16, 4598; g) S. G. Dawande,
V. Kanchupalli, J. Kalepu, H. Chennamsetti, B. S.
Lad, S. Katukojvala, Angew. Chem., Int. Ed. 2014, 53,
4076; h) Y. Liang, K. Yu, B. Li, S. Xu, H. Song, B.
Wang, Chem. Commun. 2014, 50, 6130; i) Y. Zhang,
J. Zheng, S. Cui, J. Org. Chem. 2014, 79, 6490; j) H.-
W. Lam, K.-Y. Man, W.-W. Chan, Z.-Y. Zhou, W.-Y.
Yu, Org. Biomol. Chem. 2014, 12, 4112; k) W. Ai, X.
Yang, Y. Wu, X. Wang, Y. Li, Y. Yang, B. Zhu,
Chem. Eur. J. 2014, 20, 17653; l) L.-L. Shi, K. Yu,
B.-Q. Wang, Chem. Commun. 2015, 51, 17277; m) B.
Zhou, Z. Chen, Y. Yang, W. Ai, H. Tang, Y. Wu, W.
Zhu, Y. Li, Angew. Chem. Int. Ed. 2015, 54, 12121;
n) Y. Yang, X. Wang, Y. Li, B. Zhou, Angew. Chem.
Int. Ed. 2015, 54, 15400; o) S. Sharma, S. H. Han, S.
Han, W. Ji, J. Oh, S.-Y. Lee, J. S. Oh, Y. H. Jung, I. S.
Kim, Org. Lett. 2015, 17, 2852; p) S.-J. Yu, S. Liu, Y.
Lan, B.-S. Wan, X.-W. Li, J. Am. Chem. Soc. 2015,
137, 1623; q) J. Zhou, J. Shi, X. Liu, J. Jia, H. Song,
H. E. Xu, W. Yi, Chem. Commun. 2015, 51, 5868; r)
R. B. Dateer, S. Chang, Org. Lett. 2016, 18, 68; s) D.
Das, A. Biswas, U. Karmakar, S. Chand, R. Samanta,
J. Org. Chem. 2016, 81, 842; t) Z. Qi, S. Yu, X. Li,
Org. Lett. 2016, 18, 700; u) J.-Q. Wu, Z. Yang, S.-S.
Zhang, C.-Y. Jiang, Q.-J. Li, Z.-S. Huang, H.-G.
Wang, ACS Catal. 2015, 5, 6453.
[11] a) T. Yoshino, H. Ikemoto, S. Matsunaga, M. Kanai,
Angew. Chem. Int. Ed. 2013, 52, 2207; b) T. Yoshino,
H. Ikemoto, S. Matsunaga, M. Kanai, Chem. Eur. J.
2013, 19, 9142.
[12] a) A. Lerchen, T. Knecht, C. G. Daniliuc, F. Glorius,
Angew. Chem. Int. Ed. 2016, 55, 15166; b) H. Wang,
M. M. Lorion, L. Ackermann, Angew. Chem. Int. Ed.
2016, 55, 10386; c) D. Zell, Q. Bu, M. Feldt, L.
Ackermann, Angew. Chem. Int. Ed. 2016, 55, 7408;
d) R. Mei, J. Loup, L. Ackermann, ACS Catal. 2016,
6, 793; e) A. Lerchen, S. Vasquez-Céspedes, F.
Glorius, Angew. Chem. Int. Ed. 2016, 55, 3208; f) D.-
G. Yu, T. Gensch, F. de Azambuja, S. Vásquez-
Céspedes, F. Glorius, J. Am. Chem. Soc. 2014, 136,
17722; g) J. Li, L. Ackermann, Angew. Chem. Int. Ed.
2015, 54, 8551; h) J. Li, L. Ackermann, Angew.
Chem. Int. Ed. 2015, 54, 3635; i) J. R. Hummel, J. A.
Ellman, J. Am. Chem. Soc. 2015, 137, 490; j) J. R.
Hummel, J. A. Ellman, Org. Lett. 2015, 17, 2400; k)
B. Sun, T. Yoshino, S. Matsunaga, M. Kanai, Adv.
Synth. Catal. 2014, 356, 1491; l) H. Ikemoto, T.
Yoshino, K. Sakata, S. Matsunaga, M. Kanai, J. Am.
Chem. Soc. 2014, 136, 5424; m) B. Sun, T. Yoshino,
M. Kanai, S. Matsunaga, Angew. Chem. Int. Ed. 2015,
54, 4508; n) J. Park, S. Chang, Angew. Chem. Int. Ed.
2015, 54, 12711; o) P. Patel, S. Chang, ACS Catal.
2015, 5, 853; p) M. Sen, D. Kalsi, B. Sundararaju,
Chem. Eur. J. 2015, 21, 15529; q) S. Prakash, K.
Muralirajan, C.-H. Cheng, Angew. Chem. Int. Ed.
2016, 55, 1844; r) K. Muralirajan, R. Kuppusamy, S.
Prakash, C.-H. Cheng, Adv. Synth. Catal. 2016, 358,
774; s) X. Wu, K. Yang, Y. Zhao, H. Sun, G. Li, H.
Ge, Nat. Commun. 2015, 6, 6462; t) Q.-Q. Yan, Z.-K.
Chen, Z.-X. Liu, Y.-H. Zhang, Org. Chem. Front.
2016, 3, 678; u) L. B. Zhang, X.-Q. Hao, S.-K. Zhang,
Z.-J. Liu, X.-X. Zheng, J.-F. Gong, J.-L. Niu, M.-P.
Song, Angew. Chem. Int. Ed. 2015, 54, 272; v) L.
Kong, S. Yu, X. Zhou, X. Li, Org. Lett. 2016, 18,
588; w) F. Wang, H. Wang, Q. Wang, S. Yu, X. Li,
Org. Lett. 2016, 18, 1306; x) Y. Liang, N. Jiao,
[7] For representative examples catalyzed by Ir(III), see:
a) Y. Xia, Z. Liu, S. Feng, Y. Zhang, J. Wang, J. Org.
Chem. 2015, 80, 223; b) G.-D. Tang, C.-L. Pan, X. Li,
Org. Chem. Front. 2016, 3, 87; c) Y. Li, F. Wang, S.
Yu, X. Li, Adv. Synth. Catal. 2016, 358, 880; d) R. S.
Phatake, P. Patel, C. V. Ramana, Org. Lett. 2016, 18,
292, d) S.-S. Zhang, C.-Y. Jiang, J.-Q. Wu, X.-G. Liu,
5
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Advanced Synthesis & Catalysis
Angew. Chem. Int. Ed. 2016, 55, 4035; y) X.-G. Liu,
S.-S. Zhang, C.-Y. Jiang, J.-Q. Wu, Q. Li, H. Wang,
Org. Lett. 2015, 17, 5404.
[15] CCDC 1518676 (4f) contains the supplementary
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge
Crystallographic
www.ccdc.cam.ac.uk/data_request/cif.
Data
Centre
via
[13] a) Z.-Z. Zhang, B. Liu, C.-Y. Wang, B.-F. Shi, Org.
Lett. 2015, 17, 4094; b) Z.-Z. Zhang, B. Liu, J.-W.
Xu, S.-Y. Yan, B.-F. Shi, Org. Lett. 2016, 18, 1776.
[16] H. Christian, R. Georg, S. Jean-Philippe, Z. A.
Cornelia, US2010/331318 A1, 2010.
[14] a) M. Sen, B. Emayavaramban, N. Barsu, J. R.
Premkumar, B.Sundararaju, ACS Catal. 2016, 6,
2792; b) N. Barsu, M. A. Rahman, M. Sen, B.
Sundararaju, Chem. Eur. J. 2016, 22, 9135.
[17] E. M. Simmons, J. F. Hartwig, Angew. Chem. Int. Ed.
2012, 51, 3066.
6
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10.1002/adsc.201700636
Advanced Synthesis & Catalysis
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