Iron(II) Chloride-Catalyzed Nitrene Transfer Reaction for Dearomative Amination of β-Naphthols with Aryl Azides

Article abstract of DOI:10.1002/adsc.201800810

A first example of Fe-catalyzed dearomative amination of β-naphthols with aryl azides is described. The method constructs a nitrogen-containing quaternary carbon center catalyzed by cheap and readily available iron salt FeCl₂, and affords a series of α-amino-β-naphthalenones in good to excellent yields under simple and mild reaction conditions. Preliminary experimental and computational studies suggest that the reaction is probably initiated by iron-iminyl diradical and followed by intramolecular hydrogen transfer to generate iron-aminyl radical and finally an intramolecular radical combination reaction. (Figure presented.).

Full text of DOI:10.1002/adsc.201800810

Title: Iron(II) Chloride-Catalyzed Nitrene Transfer Reaction for
Dearomative Amination of β-Naphthols with Aryl Azides
Authors: Dun-Qi Wu, Zhen-Yu Guan, Yi Peng, Jian Sun, Cheng Zhong,
and Qing-Hai Deng
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800810
Link to VoR: http://dx.doi.org/10.1002/adsc.201800810

Advanced Synthesis & Catalysis
10.1002/adsc.201800810
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Iron(II) Chloride-Catalyzed Nitrene Transfer Reaction for
Dearomative Amination of β-Naphthols with Aryl Azides
a
a
a
a
b
a
Dun-Qi Wu, Zhen-Yu Guan, Yi Peng, Jian Sun, Cheng Zhong, * Qing-Hai Deng *
a
The Education Ministry Key Lab of Resource Chemistry and Shanghai Key Laboratory of Rare Earth Functional
Materials, Shanghai Normal University, 100 Guilin Road, Shanghai 200234, P. R. China
e-mail: qinghaideng@shnu.edu.cn
College of Chemistry and Molecular Sciences, Wuhan University, 199 Bayi Road, Wuhan, Hubei 430072, P. R. China
b
e-mail: zhongcheng@whu.edu.cn
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))
Abstract: A first example of Fe-catalyzed dearomative rebound[9] to the iron-amido moiety on basis of a
amination of β-naphthols with aryl azides is described. The number of theoretical and experimental evidences. We
method constructs a nitrogen-containing quaternary carbon postulated that if a metal imido species abstracts a
center catalyzed by cheap and readily available iron salt hydrogen from O-H bond of enolate to form an enolate
[10]
FeCl , and affords a series of α-amino-β-naphthalenones in radical which could isomer to α-carbonyl radical,
2
good to excellent yields under simple and mild reaction
conditions. Preliminary experimental and computational
studies suggest that the reaction is probably initiated by iron-
iminyl diradical and followed by intramolecular hydrogen
transfer to generate iron-aminyl radical and finally an
intramolecular radical combination reaction.
the α-carbonyl radical could couple with the newly
formed iron-aminyl radical, and would therefore offer
a valuable method for constructing C-N bond. Herein,
we report the first successful example of dearomative
amination of β-naphthols with aryl azides by iron-
catalyzed nitrene transfer reaction, which constructs a
nitrogen-containing quaternary carbon center (Scheme
Keywords: iron catalysis; nitrene; radical; amination; β-
naphthol
1
). It is worth noting that cheap and commercial
available FeCl is used as catalyst, and this method
represents one of most efficient ways for the synthesis
2
[
11-13]
of
α-amino-β-naphthalenones
which
are
important structural motifs in various biologically
[14]
Nitrogen is one of the most important elements in active natural products and therapeutic reagents.
natural products and bioactive compounds. Thus,
many efforts have been put into the development of
efficient synthetic approaches to nitrogen-containing
organic compounds. Among them, transition-metal-
catalyzed nitrene transfer reaction with azides as
precursors is regarded as one of the most efficient and
atom-economic tools for the synthesis of nitrogen-
[1]
containing moleculars. However, only a few kind of
efficient nitrene transfer reactions such as C-H bond
[2]
[3]
amination, aziridination of olefins, and sulfur
imidations[ were developed (Scheme 1). Hence,
exploring the applications of such reactions in other
type of transformations to overcome some difficult
targets like constructing of nitrogen-containing
quaternary carbon center[ is an interesting but still
challenging objective.
4]
5]
Scheme 1. The types of metal catalyzed nitrene transfer
Generally, in first row transition metal catalyzed reactions.
nitrene transfer reactions, metal imido species, proved
as the key active intermediate, has been confirmed to
[
6-8]
have significant radical character.
For instance,
To test the above hypothesis, our initial studies
recent advances in the iron-catalyzed C–H amination focused on the reaction of 1, 3-dimethylnaphthalen-2-
reaction[
7, 8]
have demonstrated that the mechanism ol (1a) with 1-azido-4-methoxybenzene (2a) in the
[15]
involves a hydrogen atom abstraction (HAA) from C– presence of iron catalyst
(Table 1). When the
H bonds by iron-imido species followed by radical reaction was carried out in 1, 2-dichloroethane (DCE)
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201800810
at room temperature in the presence of FeCl
2
(10
Various β-naphthol derivatives (1a-1t) were reacted
mol%), the desired product 3aa was obtained only in with 1-azido-4-methoxybenzene (2a) under the
1
2% yield. Fortunately, the reaction temperature optimal conditions to examine the generality of the
1
affected the yield dramatically, which was increased to process (Table 2). R on the 1-position of 3-methyl-2-
o
9
9% when the reaction was carried out at 80 C (entries naphthol derivatives were firstly screened. Aliphatic
, 3). Fe(OAc) showed no catalytic activity and groups (ethyl, n-butyl) were well tolerated and the
only afforded the product in 20% yield bulkier group (n-butyl) afforded the slightly decreased
entries 4, 5). Solvent screening showed that DCE and yield (87%) (3ba, 3ca). Notably, MeCN in place of
2
2
Fe(OTf)
(
2
MeCN were both suitable for this reaction (entries 3 DCE was used as the optimal solvent for the substrates
and 6–11). Reducing the catalyst loading to 5 mol% with an aryl group at 1-position of naphthols. The
and the usage of azide 2a to 2.5 equivalent both phenyl groups bearing electron-donating substituents
resulted in lower yields (entries 12, 13). As expected, at 1-position were all well tolerated, affording the
there was no product generated without FeCl
4) and a similar comparable result (97% yield) was 96%) by prolonging the reaction time. In contrast, the
obtained in the presence of ultrapure FeCl , thus substrates with electron-withdrawing phenyl group
suggesting that the catalyst system is iron based (entry afforded the desired products in lower yields (3ja-3la,
2
(entry dearomatized products (3da-3ia) in high yields (89%-
1
2
1
5). Notably, a comparable product yield (93% yield) 61%-89%). 1-Allyl-3-methylnaphthalen-2-ol only
was found when the reaction was conducted under an gave the corresponding product 3ma with 53% yield.
2
atmosphere of air (entry 16). Based on these R at the 3-position was then tested. 1-Methyl-2-
optimization experiments, entry 3 was identified as the naphthol derivatives bearing 3-Bn (1n), 3-Cl (1o), 3-
optimal conditions for the substrate scope Br (1p), 3-I (1q), as well as 3-H (1r) generally led to
investigations.
the desired products in excellent yields (94% - 99%).
Furthermore, different groups on the aromatic ring of
1, 3-dimethyl-2-naphthol such as 6-methyl (1s) and 7-
methoxy(1t) substituents also afforded the product 3sa
Table 1. Optimization of reaction conditions. a)
(
97%) and 3ta (99%) in excellent yields, respectively.
The molecular structures of products were confirmed
[16]
by the X-Ray diffraction analysis of 3da.
Unfortunately, 2,6-disubstituted phenols such as 2, 6-
dimethylphenol (1u) and 2, 4, 6-trimethylphenol (1v)
proved to be unreactive under these reaction conditions.
Entry Catalyst
Solvent Temp Time Yieldb)
o
(
C)
(h)
39
22
11
24
24
28
11
11
11
11
11
11
18
48
11
22
(%)
Table 2. Substrate scope of β-naphthols.
1
2
3
4
5
6
7
8
9
1
FeCl
FeCl
FeCl
2
2
2
DCE
DCE
DCE
DCE
DCE
DCM
THF
PhMe
25
60
80
80
80
40
80
80
12
86
99
Fe(OAc)
Fe(OTf)
2
trace
20
2
FeCl
FeCl
FeCl
FeCl
FeCl
FeCl
FeCl
FeCl
--
2
2
2
2
2
2
2
2
71
68
66
Dioxane 80
82
0
MeCN
DMSO
DCE
80
80
80
80
80
80
80
97
11
46
c)
d)
1
1
1
1
1
2
3
4
5
6
78
DCE
90
NRe)
DCE
f)
FeCl
2
2
DCE
97
g)
FeCl
DCE
93
a)
Reaction were conducted with 1a (0.20 mmol), 2a (0.60
o
mmol), catalyst (10 mol%) and solvent (1 mL) at 80 C under
the atmosphere of argon. Yields of isolated products.
mol% of FeCl
Reaction. Ultrapure FeCl (99.998% based on trace metals,
Sigma-Aldrich) was used. The reaction was carried out
under the atmosphere of air.
b)
c)
5
d)
e)
2
was used. 2.5 equiv of 2a was used. No
f)
2
g)
a)
MeCN instead of DCE as solvent.
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201800810
Various substituted aryl azides (2) were
subsequently tested in this reaction (Table 3).
Reactions of 1, 3-dimethyl-2-naphthol with aryl azides
bearing electron-withdrawing and -donating groups
were carried out smoothly to give the desired products
(
3ab-3aj) in high yields (85% - 91%). Unfortunately,
other kinds of azides, such as 4-methylbenzenesulfonyl
azide (TsN ), benzyl azide and benzoyl azide, proved
to be unreactive under these reaction conditions.
3
Table 3. Substrate scope of azides.
Scheme 2. Gram-scale reaction and further transformation
of the products.
In order to understand the reaction mechanism,
several control experiments were carried out as
described in Scheme 3. The reaction in the presence of
a
radical
quencher
2,2,6,6-tetramethyl-1-
piperidinyloxy (TEMPO) under the optimal reaction
conditions were completely suppressed, and the
addition of a radical inhibitor such as 2, 6-di-tert-butyl-
4
-methylphenol (BHT) or 1,1-diphenylethylene
(
DPE) dramatically inhibited the reaction to afford the
To highlight the utility of this method, a gram scale
reaction and further transformations of the 2-
naphthalenone products have been carried out (Scheme
desired product in 52% or 61% yield, respectively (eq.
a, Scheme 3). These results, including complete
inhibition for TEMPO as well as partial quenching for
BHT and DPE, suggest that the process probably
involves a radical pathway and the intermediate might
2
). The reaction of 1a with 2a could be scaled up to
gram quantities smoothly and provided 3aa (1.72 g) in
8% yield. The products with carbon-halogen bond
9
[17]
be an intramolecular or tight radical pair.
Furthermore, the reaction of naphthalen-2-ol (7) with
-azido-4-methoxybenzene (2a) under the standard
(
3qa, 3ai, 3ag) could be coupled with alkynes
smoothly through Sonogashira reaction to generate the
corresponding products (4, 5, 6) in high yields.
1
conditions was carried out to obtain the coupling
product 8 in 82% yield which is probably formed
through dimerization of less hindered radical species
(
eq. b, Scheme 3), but the reaction with 2-
methoxynaphthalene (10) as the substrate did not work
at all (eq. c, Scheme 3). These investigations indicate
that the hydroxyl group of the substrate is crucial to the
reaction and iron-imido species does not insert 1-
position of naphthols directly.
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201800810
spin natural orbitals, spin density plots, population of
atomic charge and spin, Mayer bond order of all
species and detailed analysis of electronic structures of
1
2 and 13a are in part V of SI) In this plausible
mechanism, we considered that hydrogen atom
abstraction (HAA) proceeded via a concerted (single-
step) proton/electron transfer. However, the possibility
of stepwise proton/electron transfer could not be
excluded. We also proposed an alternative plausible
mechanism in the Supporting Information.
Scheme 3. Control experiments for mechanistic
investigations.
Based on the above experimental results and
[18]
previous related reports, we further performed DFT
calculations[ to investigate the reaction mechanism.
The energy profiles of plausible reaction pathway are
shown in Figure 1. In the initial step, azide 2a and
19]
substrate 1a react with FeCl to generate the iron-
2
azide-substrate complex 11. Nitrogen is then liberated
from 11 through transition state TS1 with a barrier of
1
19.1 kJ/mol to give 12. Wave function analysis
indicate that 12 is an iron-iminyl complex with singlets
diradical character. As shown in Figure 1c and 1d, the
unpaired α electron on nitrene is stabilized by
(
conjugate with) d orbitals of iron and unpaired β
electron on nitrene is stabilized by (conjugate with)
both d orbitals of iron and π orbitals of
methoxybenzene group. In transition state TS2, the
iminyl radical abstracts hydrogen from hydroxyl group
atom via its α electron. The barrier of this step is 36.3
kJ/mol. The resulting iron-aminyl radical 13a has an
unpaired β electron that has the distribution similar to
that of 12. After conformational change to 13b, where
the methoxybenzene group forms π-π stacking with the
naphthol, the aminyl radical attacks the α-position of
naphthol to give the intermediate 14 via transition state
TS3. The free energy barrier for this step is 28.6 kJ/mol.
Finally, de-coordination from intermediate 14 liberates
the product 3a and regenerates the catalyst. The
amination at β-postion of naphthol was also calculated,
the results are shown in part V.2 of SI, where the
barrier is 78.9 kJ/mol and the energy of β-aminated
complex 14-β is 106.3 kJ/mol higher than that of 14.
These results are consistent with experiments and
confirms that the reaction aminated C-α position
regiospecifically. Obviously, the rate-determine step is
the nitrene formation (nitrogen leaving) step from 11
to 12. The subsequent steps that have radical character
have much lower barrier and are intramolecular
reactions, which explain why the radical inhibitor has
limited effects on the final yield. (the nature orbitals,
Figure 1. a) The calculated reaction pathway. b) Proposed
mechanism. c) Schematic orbital interaction of 12. d) Spin
density plot of 12 and 13a.
In conclusion, we have successfully developed an
efficient and practical Fe-catalyzed dearomative
amination of β-naphthnols for constructing a nitrogen-
containing quaternary carbon center under mild
conditions. The reaction generates series of α-amino-
β-naphthalenones in high yields up to 99% and can be
readily scaled up to gram amounts. Experimental and
DFT calculations found that iron-iminyl complex
formed by iron-azide denitrogenation is a singlet
diradical nitrene species. One of the radicals abstracts
hydrogen from hydroxyl group, and the other one is
responsible for the following dearomatization of β-
naphthols via an intramolecular radical combination
reaction. Further studies on the applications of this
protocol are ongoing in our group.
4
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Advanced Synthesis & Catalysis
10.1002/adsc.201800810
Experimental Section
M. Weldy, S. B. Blakey, C. E. MacBeth, Chem. Sci. 2015,
6
, 6672-6675; c) E. R. King, G. T. Sazama, T. A. Betley,
2
A typical experimental procedure: 1 (0.2 mmol), FeCl (0.02
J. Am. Chem. Soc. 2012, 134, 17858-17861; d) V.
Lyaskovskyy, A. I. O. Suarez, H. Lu, H. Jiang, X. P.
Zhang, B. de Bruin, J. Am. Chem. Soc. 2011, 133, 12264-
12273; Cu: e) J. Peng, Z. Xie, M. Chen, J. Wang, Q. Zhu,
Org. Lett. 2014, 16, 4702-4705; f) Y. M. Badiei, A.
Dinescu, X. Dai, R. M. Palomino, F. W. Heinemann, T.
R. Cundari, T. H. Warren, Angew. Chem. 2008, 120,
mmol), 2 (0.6 mmol) and solvent (1 mL) were added into a
Schlenk tube successively at nitrogen atmosphere. The
mixture was stirred at 80℃. After the complete
disappearance of 1 demonstrated by TLC, the mixture was
concentrated under reduced pressure and the residue was
purified
by
column
chromatography
(ethyl
acetate/petroleum ether) to afford the desired product 3.
1
9
0109-10112; Angew. Chem. Int. Ed. 2008, 47, 9961-
964; Mn: g) S. M. Paradine, J. R. Griffin, J. Zhao, A. L.
Acknowledgements
Petronico, S. M. Miller, M. Christina White, Nat. Chem.
015, 7, 987-994; Ni: h) S. Wiese, J. L. McAfee, D. R.
Financial support from the Program of the Professor of Special
Appointment (Eastern Scholar) at Shanghai Institutions of Higher
Learning, the National Natural Science Foundation of China (no.
2
Pahls, C. L. McMullin, T. R. Cundari, T. H. Warren, J.
Am. Chem. Soc. 2012, 134, 10114-10121.
2
1402119, 21772122, 51203121), and Shanghai Rising-Star
Program (no. 16QA1403100) are greatly appreciated.
[
[
7] For selected reviews of iron catalyzed nitrene transfer
reactions, see: a) L. Zhang, L. Deng, Chin. Sci. Bull.
2
M. Wong, Top Organomet. Chem. 2011, 33, 111-138.
012, 57, 2352-2360; b) C.-M. Che, C.-Y. Zhou, E. L.-
References
[
1] For selected reviews on nitrene transfer reaction, see: a)
B. Darses, R. Rodrigues, L. Neuville, M. Mazurais, P.
Dauban, Chem. Commun. 2017, 53, 493-508; b) T.
Xiong, Q. Zhang, Chem. Soc. Rev. 2016, 45, 3069-3087;
c) E. Gras, S. Chassaing, Org. React. Mech. 2015, 171-
8] a) T. Yang, X. Fan, X. Zhao, W. Yu, Org. Lett. 2018, 20,
1
875-1879; b) I. T. Alt, C. Guttroff, B. Plietker, Angew.
Chem. 2017, 129, 10781-10722; Angew. Chem. Int. Ed.
017, 56, 10582-10586; c) C. K. Prier, R. K. Zhang, A.
R. Buller, S. Brinkmann-Chen, F. H. Arnold, Nat. Chem.
017, 9, 629-634; d) B. Bagh, D. L. J. Broere, V. Sinha,
2
2
1
2
08; d) T. Uchida, T. Katsuki, Chem. Rec. 2014, 14, 117-
29; e) T. A. Ramirez, B. Zhao, Y. Shi, Chem. Soc. Rev.
012, 41, 931-942; f) G. Dequirez, V. Pons, P. Dauban,
2
P. F. Kuijpers, N. P. van Leest, B. de Bruin, S. Demeshko,
M. A. Siegler, J. I. van der Vlugt, J. Am. Chem. Soc. 2017,
1
Angew. Chem. 2012, 124, 7498-7510; Angew. Chem. Int.
Ed. 2012, 51, 7384-7395; g) J. L. Roizen, M. E. Harvey,
J. Du Bois, Acc. Chem. Res. 2012, 45, 911-922; h) J. W.
W. Chang, T. M. U. Ton, P. W. H. Chan, Chem. Rec.
39, 5117-5124; e) D. A. Iovan, M. J. T. Wilding, Y.
Baek, E. T. Hennessy, T. A. Betley, Angew. Chem. 2017,
1
1
2
1
29, 15805-15808; Angew. Chem. Int. Ed. 2017, 56,
5599-15602; f) I. T. Alt, B. Plietker, Angew. Chem.
016, 128, 1542-1545; Angew. Chem. Int. Ed. 2016, 55,
519-1522; g) N. C. Thacker, Z. Lin, T. Zhang, J. C.
2
2
011, 11, 331-357; i) T. G. Driver, Org. Biomol. Chem.
010, 8, 3831-3846; j) S. Fantauzzi, A. Caselli, E. Gallo,
Dalton Trans. 2009, 5434-5443; k) P. Mueller, C. Fruit,
Chem. Rev. 2003, 103, 2905-2919.
Gilhula, C. W. Abney, W. Lin, J. Am. Chem. Soc. 2016,
1
2
38, 3501-3509; h) E. T. Hennessy, T. A. Betley, Science
013, 340, 591-595; i) Y. Liu, X. Guan, E. L.-M. Wong,
[
[
2] For selected reviews of nitrene transfer reactions for C–
H insertion reactions, see: a) F. Collet, C. Lescot, C.
Liang, P. Dauban, Dalton Trans. 2010, 39, 10401-
P. Liu, J.-S. Huang, C.-M. Che, J. Am. Chem. Soc. 2013,
35, 7194-7204; j) Q. Nguyen, T. Nguyen, T. G. Driver,
1
J. Am. Chem. Soc. 2013, 135, 620-623; k) E. R. King, E.
T. Hennessy, T. A. Betley, J. Am. Chem. Soc. 2011, 133,
4
1
4
0413; b) H. M. L. Davies, J. R. Manning, Nature 2008,
51, 417-424.
917-4923; l) J. Bonnamour, C. Bolm, Org. Lett. 2011,
3, 2012-2014; m) Y. Liu, J. Wei, C.-M. Che, Chem.
3] For selected reviews of aziridination of olefins, see: a) L.
1
Degennaro, P. Trinchera, R. Luisi, Chem. Rev. 2014, 114,
Commun. 2010, 46, 6926-6928; n) Y. Liu, C.-M. Che,
Chem. Eur. J. 2010, 16, 10494-10501; o) S. Jana, M. D.
Clements, B. K. Sharp, N. Zheng, Org. Lett. 2010, 12,
7
1
881-7929; b) H. Pellissier, Adv. Synth. Catal. 2014, 356,
899-1935.
3
1
736-3739; p) M. Shen, T. G. Driver, Org. Lett. 2008,
0, 3367-3370.
[
[
4] V. Bizet, C. M. M. Hendriks, C. Bolm, Chem. Soc. Rev.
015, 44, 3378-3390.
2
[
[
9] a) P. F. Kuijpers, J. I. van der Vlugt, S. Schneider, B. de
Bruin, Chem. Eur. J. 2017, 23, 13819-13829; b) P. R.
Ortiz de Montellano, Chem. Rev. 2010, 110, 932-948.
5] For selected reviews of constructing of nitrogen-
containing quaternary carbon center, see: a) J. Clayden,
M. Donnard, J. Lefranc, D. J. Tetlow, Chem. Commun.
2
011, 47, 4624-4639; b) M. Shibasaki, M. Kanai, Chem.
10] a) N. Gonzalez-Rivas, A. Cedillo, Int. J. Quantum
Chem. 2009, 109, 1031-1035; b) M. Pouliot, P. Renaud,
K. Schenk, A. Studer, T. Vogler, Angew. Chem. 2009,
Rev. 2008, 108, 2853-2873; c) D. J. Ramon, M. Yus,
Curr. Org. Chem. 2004, 8, 149-183.
1
6
21, 6153-6156; Angew. Chem. Int. Ed. 2009, 48, 6037-
040; c) K. Miura, N. Fujisawa, H. Saito, D. Wang, A.
[
6] For selected examples of first row transition metal
catalyzed nitrene transfer reactions, Co: a) M. Goswami,
V. Lyaskovskyy, S. R. Domingos, W. J. Buma, S.
Woutersen, O. Troeppner, I. Ivanovic-Burmazovic, H.
Lu, X. Cui, X. P. Zhang, E. J. Reijerse, S. DeBeer, M. M.
van Schooneveld, F. F. Pfaff, K. Ray, B. de Bruin, J. Am.
Chem. Soc. 2015, 137, 5468-5479; b) O. Villanueva, N.
Hosomi, Org. Lett. 2001, 3, 2591-2594.
[
11] D. Sarkar, M. K. Ghosh, N. Rout, P. Kuila, New J.
Chem. 2017, 41, 3715-3718.
5
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Advanced Synthesis & Catalysis
10.1002/adsc.201800810
[
[
12] a) J. J. Farndon, X. Ma, J. F. Bower, J. Am. Chem. Soc.
017, 139, 14005-14008; b) X. Ma, J. J. Farndon, T. A.
Young, N. Fey, J. F. Bower, Angew. Chem. 2017, 129,
2
1
1
4723-14727; Angew. Chem., Int. Ed. 2017, 56, 14531-
4535.
13] a) A. Changotra, S. Das, R. B. Sunoj, Org. Lett. 2017,
9, 2354-2357; b) S.-G. Wang, Q. Yin, C.-X. Zhuo, S.-
1
L. You, Angew. Chem. 2015, 127, 657-660; Angew.
Chem., Int. Ed. 2015, 54, 647-650; c) J. Nan, J. Liu, H.
Zheng, Z. Zuo, L. Hou, H. Hu, Y. Wang, X. Luan, Angew.
Chem. 2015, 127, 2386-2390; Angew. Chem. Int. Ed.
2
015, 54, 2356-2360; d) X. Lian, L. Lin, G. Wang, X.
Liu, X. Feng, Chem. Eur. J. 2015, 21, 17453-17458.
[
14] a) J. T. Randolph, C. A. Flentge, P. P. Huang, D. K.
Hutchinson, L. L. Klein, H. B. Lim, R. Mondal, T.
Reisch, D. A. Montgomery, W. W. Jiang, S. V. Masse,
L. E. Hernandez, R. F. Henry, Y. Liu, G. Koev, W. M.
Kati, K. D. Stewart, D. W. A. Beno, A. Molla, D. J.
Kempf, J. Med. Chem. 2009, 52, 3174-3183; b) F.
Bevalot, M. Leboeuf, A. Bouquet, A. Cave, Ann. Pharm.
Fr. 1977, 35, 65-72; c) W. M. Harris, T. A. Geissman, J.
Org. Chem. 1965, 30, 432-434.
[
[
15] The detailed date for screening of other transition
metals, see the Supporting Information.
16] CCDC 1815117 (3da) contains the supplementary
crystallographic data for this paper. The data can be
obtained free of charge from The Cambridge
Crystallographic Data Centre.
[
[
17] a) G. Bassioni, F. H. Koehler, Eur. J. Org. Chem. 2006,
2
795-2802; b) C. A. A. Ruiz, V. G. Toscano, D. de B.
Rezende, W. J. Baader, Tetrahedron Lett. 2001, 42,
613-2615; c) R. S. Givens, L. Strekowski, R.
2
Devonshire, J. Am. Chem. Soc. 1974, 96, 1631-1633.
18] a) M. J. T. Wilding, D. A. Iovan, A. T. Wrobel, J. T.
Lukens, S. N. MacMillan, K. M. Lancaster, T. A. Betley,
J. Am. Chem. Soc. 2017, 139, 14757-14766; b) Q. Zhang,
C. Wu, L. Zhou, J. Li, Organometallics 2013, 32, 415-
4
26; c) R. E. Cowley, N. A. Eckert, S. Vaddadi, T. M.
Figg, T. R. Cundari, P. L. Holland, J. Am. Chem. Soc.
011, 133, 9796-9811.
2
[
19] The geometries and frequencies were calculated at
M062X-D3/def2-SVP level and then the single points
were calculated at M062X-D3/def2-TZVP level. SMD
solvation model was used using dichloroethane as
solvent. All DFT calculations were performed using
Gaussian 09 software and wave function analyses were
performed using Multiwfn software.
6
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