Nickel-Catalyzed Deoxygenative Deuteration of Aryl Sulfamates

Article abstract of DOI:10.1002/adsc.201601105

The nickel-catalyzed deoxygenative deuteration of aryl/heteroaryl sulfamates has been developed, and the effective incorporation of deuterium into a variety of aromatic compounds was achieved with sufficient catalytic efficiency and high deuteration degree. This process tolerated reducible functional moieties and heterocyclic structures. Additionally, a double introduction of deuterium also successfully gave a desired product with a high yield and deuterium content. (Figure presented.).

Full text of DOI:10.1002/adsc.201601105

UPDATES
DOI: 10.1002/adsc.201601105
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
Nickel-Catalyzed Deoxygenative Deuteration of Aryl Sulfamates
a,
a
a
a,
Masami Kuriyama, * Shota Kujirada, Kotaro Tsukuda, and Osamu Onomura *
a
Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521, Japan
Fax: (+81)-95-819-2476; e-mail: mkuriyam@nagasaki-u.ac.jp; onomura@nagasaki-u.ac.jp
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
Received: October 8, 2016; Revised: December 2, 2016; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201601105
row transition metals as promising catalysts because of
Abstract: The nickel-catalyzed deoxygenative deut-
eration of aryl/heteroaryl sulfamates has been
their advantageous features, such as a lower level of
[
13,14]
costs and high natural abundance.
Among these
developed, and the effective incorporation of
deuterium into a variety of aromatic compounds
was achieved with sufficient catalytic efficiency and
high deuteration degree. This process tolerated
reducible functional moieties and heterocyclic
structures. Additionally, a double introduction of
deuterium also successfully gave a desired product
with a high yield and deuterium content.
base metals, nickel has played a significant role in
[
15]
industrial applications,
and the distinctive homo-
geneous catalysis has contributed to the progress of
[
16,17]
catalytic transformation.
Meanwhile, phenol de-
rivatives are less expensive, easily available, and highly
diverse compounds, while the ingenuity for phenolic
hydroxyl groups is often required for the deoxygena-
[
18]
tive transformation. Aryl sulfamates have attracted
much interest by reason of their facile preparation,
pronounced stability, and easy functionalization via
Keywords: Arenes; Deoxygenation; Deuteration;
Nickel; Sulfamates
[
19]
ortho or para metalation. Therefore, we envisaged
that an attractive deuteration system would be given
by the combined use of nickel catalysts and sulfamoy-
[
20]
Catalytic deuteration of organic molecules is a key lated phenols.
Herein, we report the nickel-cata-
process because deuterated compounds are used in lyzed deoxygenative deuteration of aryl sulfamates
extensive investigation such as the metabolic analysis employing an unsymmetrical NHC ligand.
of bioactive agents as well as the mechanistic study of
[1]
various reactions. In addition, increasing interest has
been recently focused on the site-specific introduction
of deuterium into pharmaceutical molecules owing to
its beneficial effects to improve their therapeutic
[2]
profiles.
In particular, the catalytic deuteration
methods for aryl groups are highly important on the
ground of their ubiquity in pharmaceutical and
[3]
bioactive agents. As a typical deuterium incorpora-
tion into aromatic compounds, metal-catalyzed H/D
exchange has made rapid strides, in which multiple
deuteration in a molecule is basically promoted by
precious metal catalysts depending on the respective
[
4,5,6]
reactivity of reactive sites.
On the other hand,
deuterodefunctionalization is also known as a power-
[
7]
ful transformation, and a few kinds of the catalytic
methods for aromatics have been developed, such as
[
8]
[9]
[10]
deborylative , decarboxylative , deoxygenative
,
[
11,12]
and dehalogenative
deuteration. In these process-
es, precious metals were principally used as catalysts, Scheme 1. Metal-catalyzed deuterodefunctionalization for ar-
such as palladium, silver, iridium, and gold, although a omatic compounds.
[
9b]
copper-catalyzed deuterodecarboxylation
was re-
ported as an exceptional and developing approach
(Scheme 1). In recent years, focus has shifted to first-
Adv. Synth. Catal. 2016, 358, 1–7
1
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
[
a]
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
Table 1. Optimization of Reaction Conditions.
Entry
Ligand
Ni
Base
Solvent
Yield [%]
D content [%]
1
2
3
4
5
6
7
8
9
none
L1
L2
L3
L4
L5
L6
L7
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh
Ni(1-naph)Cl(PPh
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh3)2
NiCl2
K PO
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
dioxane
DMA
0
ND
98
99
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
K PO
59
63
75
63
86
64
84
4
3
)
)
K
K
PO
3
PO
3
3
2
>99
>99
>99
>99
>99
87
ND
ND
88
3
2
K PO
3
K PO
3
K PO
3
K PO
3
Cy P·HBF
K PO
3
4
3
1
1
1
1
1
15
16
17
18
0
1
2
3
4
t-Bu P·HBF
K PO
0
0
1
3
4
3
L5
L5
L5
L5
L5
L5
L5
L5
L5
L5
L5
L5
K PO
3
Ni(OTf)2
Ni(COD)2
K PO
3
K PO
27
trace
trace
14
0
trace
trace
74
39
0
93
3
Ni[P(OPh)3]2
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh
Ni(1-naph)Cl(PPh
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh3)2
Ni(1-naph)Cl(PPh3)2
K PO
ND
ND
>99
ND
ND
ND
>99
60
3
Na PO
3
4
Cs CO
2
3
)
)
K
CO
2
3
2
3
Na CO
2
KF
3
2
3
19
20
21
22
K PO
3
4
4
4
K PO
3
K PO
3
DMSO
ND
[
a]
Reaction conditions: 1a (1 mmol), 2a (1.2 equiv.), ligand (6 mol%), Ni (3 mol%), base (2 equiv.), solvent (2 mL), 1108C,
15 h. D content was determined by H-NMR (500 MHz).
1
Initially, optimization of reaction conditions for ligand precursors were found to be necessary for high
deoxygenative deuteration was conducted in the pre- catalyst performance (entries 6–7). The evaluation of
sence of a nickel catalyst (3 mol%) with sulfamate 1a phosphine ligands unexpectedly revealed that the use
(1 mmol) and D source 2a (1.2 equiv.) as model of Cy P·HBF and t-Bu P·HBF gave a highly sig-
substrates (Table 1). The nickel-catalyzed deoxyge- nificant decrease in yield (entries 9–10), which are
native deuteration with no additional ligand never known as effective ligands for nickel-catalyzed reac-
proceeded (entry 1). Unsymmetrical NHC ligand pre- tions with sulfamates.
cursors (Scheme 2), which were readily prepared as sources, most of zero- and divalent nickel complexes
stable solids with a simple two-step procedure, were did not provide sufficient catalytic activity (entries 11–
3
4
3
4
[
20]
In the screening of nickel
[
22]
examined (entries 2–8), because we recently found 14), although Ni(1-naph)Cl(PPh3)2
that this type of NHC ligand design showed positive tionally suitable for this transformation (entry 6).
effects in transition metal-catalyzed reactions.
was excep-
[
11d,21]
Subsequently, the examination of a series of bases also
Compared with NHC precursors bearing a di- or afforded fewer options. Inorganic carbonates as well
triisopropylated phenyl moiety (entries 2–3), less as sodium phosphate tribasic and potassium fluoride
bulky ligand precursor L3 gave a better result in yield were almost ineffective (entries 15–19), and potassium
and D content (entry 4). Therefore, a series of NHC phosphate tribasic proved to be a reagent of choice
precursors with a monoalkylated phenyl ring were (entry 6). Some kinds of solvents such as toluene, 1,4-
applied (entries 5–8). Basically, ligand precursors with dioxane, DMA, DMSO were examined (entries 6 and
a less bulky substituent led to higher yields, and 20–22), and toluene led to better results in terms of
imidazolium salt L5 proved to be a superior NHC both yield and D content.
ligand precursor to afford the desired product 3a in
Influence of sulfonate leaving groups and a-deu-
86% yield and >99% D, in which the formation of terioalcohols as D sources in the nickel-catalyzed
benzophenone was observed (entry 6). In addition, deoxygenative deuteration was investigated (Table 2).
methyl groups at the 4- and 5-position in this kind of In comparison with an aryl sulfamate (entry 3), the
Adv. Synth. Catal. 2016, 358, 1–7
2
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
deuteration reaction with an aryl tosylate gave a
relatively lower yield (entry 2), whereas the use of an
aryl mesylate resulted in a significant decrease in yield
(entry 1). In the examination of a-deuterioalcohols
2a–d, the lower reactivity of D sources was observed
as the number of alkyl substituents at the a-position
increased (entries 4 and 6). In the case of a-trifluor-
omethylated D source 2c, no desired deuterated
product was obtained (entry 5).
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
Investigation of varying aryl/heteroaryl sulfamates
in the nickel-catalyzed deoxygenative introduction of
deuterium was conducted (Table 3). An electron-rich
aryl sulfamate bearing benzyloxy moiety showed high
reactivity without reductive deprotection of a benzyl
group (3b). In the presence of a coordinating amino
group, a high yield was observed with enhanced
reaction conditions (3c), while the use of a substrate
with a thioether moiety led to 57% yield (3d). Steric
hindrance close to a reactive site did not give a
significant decrease in yield, and the desired product
3e was obtained in 75% yield. Electron-withdrawing
functional groups such as acetyl and cyano group
proved to be suitable to this deuteration method
without reductive side reactions (3f and 3g). An aryl
sulfamate with a reducible alkenyl moiety was also
tried out to provide 76% yield (3h). The deuteration
with substrates including an ester group efficiently
proceeded even in gram-scale despite the concern
about transesterification (3i), and a double incorpo-
ration of deuterium was also achieved (3j). In addition
to a tertiary amide group (3k), a secondary amide
moiety was acceptable even in the presence of a free
NH group (3l). Subsequently, some kinds of the
heterocycle-containing sulfamates were examined
(3m–o). A substrate with a piperazine moiety was
deuterated with adequate efficiency, giving the desired
product in a high yield (3m). A N,N-dimethyl-
sulfamoyloxy group on a quinoline core was smoothly
replaced with a deuterium atom (3n). A dihydro-
benzofuran derivative was additionally found to be a
good reaction partner (3o). The deuterium introduc-
tion for a sulfamoylated compound 1p derived from
estrone was carried out to lead to 81% yield (3p). In
these examinations, almost quantitative D-incorpora-
tions were observed as well as high selectivity and
functional group tolerance as distinctive features.
Scheme 2. Unsymmetrical NHC ligand precursors.
Table 2. Influence of leaving groups and D sources.
Entry
R
D source
Yield
%]
D content
[%]
[
1
2
3
4
5
6
Me
p-Tol
NMe2
NMe
NMe2
2a
2a
2a
2b
2c
2d
36
77
86
67
0
99
>99
>99
>99
ND
>99
2
NMe2
37
The deuterium introduction for 1i also proceeded mate to a Ni(0) complex proceeds, leading to an aryl-
readily in the presence of a radical scavenger, such as nickel intermediate. After the displacement of a N,N-
2,6-di-tert-butyl-4-methylphenol (BHT) (Scheme 3), dimethylsulfamate anion is promoted by a base, an a-
which suggested that this reaction might not include a deuterioalkoxy-nickel species is converted to an aryl-
single electron transfer process. On the basis of the nickel-deuteride complex through b-deuterium elimi-
observation of deuterium transfer from 2a with the nation with the formation of benzophenone. Finally,
formation of benzophenone in addition to the result reductive elimination gives a deuterated product, and
of a radical trapping experiment, a tentative reaction a Ni(0) catalyst is regenerated. A similar reaction
mechanism for this nickel-catalyzed deoxygenative mechanism was recently proposed for a palladium-
[23]
deuteration of aryl sulfamates is shown in Scheme 4. catalyzed reductive cleavage of tosylated arene.
In the first step, oxidative addition of an aryl sulfa-
Adv. Synth. Catal. 2016, 358, 1–7
3
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
Table 3. Scope of substrates.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
Scheme 4. Plausible reaction mechanism.
deutertated aromatics were obtained with high D
contents. In this process, reducible functional groups
were well tolerated, and a double deuteration was also
successfully attained. Moreover, heterocycle-contain-
ing substrates in addition to a sulfamoylated estrone
were transformed with adequate efficiency. We believe
this method would contribute to the progress of the
precisely-controlled introduction of deuterium re-
quired in drug development.
Experimental Section
General Procedure for Nickel-Catalyzed
Deoxygenative Deuteration of Aryl Sulfamates
Under an argon atmosphere, a reaction tube was charged
with L5 (23.0 mg, 0.06 mmol), Ni(1-naph)Cl(PPh ) (22.4 mg,
3
2
0
.03 mmol), and K PO (425 mg, 2.0 mmol). After toluene
3 4
(2.0 mL) was added, the mixture was stirred for 15 min at
[
[
[
[
[
[
a]
b]
c]
d]
e]
f]
808C. Then, aryl sulfamate 1 (1.0 mmol) and a-deuteriobenz-
hydrol 2a (222 mg, 1.2 mmol) were added at room temper-
ature. The reaction mixture was stirred for 15 h at 1108C,
and then cooled to room temperature. After water was
added, the resulting mixture was extracted with AcOEt. The
combined organic layers were dried over MgSO . Concen-
tration and purification through silica gel column chromatog-
raphy gave a desired product.
Catalyst (5 mol%).
K PO (2.5 equiv.).
3
4
K PO (3.5 equiv.).
3
4
2
a (1.5 equiv.).
8
h.
4
Gram-scale reaction (1i: 8 mmol).
Catalyst (5 mol%), K PO (3.0 equiv.), 2a (2.4 equiv.).
[g]
3
4
Acknowledgements
This research was supported by JSPS and MEXT KAKENHI
(15K07862, 16K08167, and 26105746) and Research Grant
for Pharmaceutical Sciences from Takeda Science Founda-
tion.
Scheme 3. Deuteration in the presence of BHT.
References
[1] a) T. Furuta, H. Takahashi, Y. Kasuya, J. Am. Chem.
Soc. 1990, 112, 3633–3636; b) L. R. Hall, R. P. Hanzlik,
J. Biol. Chem. 1990, 265, 12349–12355; c) I. A. Davido-
va, L. M. Gieg, M. Nanny, K. G. Kropp, J. M. Suflita,
Appl. Environ. Microbiol. 2005, 71, 8174–8182;
In summary, a catalytic deoxygenative deuteration
of aryl sulfamates was achieved with an NHC-ligated
nickel catalyst. The deuterium introduction proceeded
with sufficient catalytic activity, and a variety of
Adv. Synth. Catal. 2016, 358, 1–7
4
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
d) M. Z.-D. Iuliis, R. H. Morris, J. Am. Chem. Soc. 2009,
131, 11263–11269.
2] a) K. Sanderson, Nature 2009, 458, 269; b) S. L. Harbe-
son, R. D. Tung, Annu. Rep. Med. Chem. 2011, 46, 403–
Maegawa, Y. Monguchi, H. Sajiki, Chem. Eur. J. 2007,
13, 1432–1441.
[
[11] Cl/D exchange: a) H. Sajiki, T. Kurita, H. E saki, F.
Aoki, T. Maegawa, K. Hirota, Org. Lett. 2004, 6, 3521–
3523; b) T. Kurita, F. Aoki, T. Mizumoto, T. Maejima,
H. Esaki, T. Maegawa, Y. Monguchi, H. Sajiki, Chem.
Eur. J. 2008, 14, 3371–3379; c) C. S. Donald, T. A. Moss,
G. M. Noonan, B. Roberts, E. C. Durham, Tetrahedron
Lett. 2014, 55, 3305–3307; d) M. Kuriyama, N. Hamagu-
chi, G. Yano, K. Tsukuda, K. Sato, O. Onomura, J. Org.
Chem. 2016, 81, 8934-8946.
4
2
17; c) N. A. Meanwell, J. Med. Chem. 2011, 54, 2529–
591; d) T. G. Gant, J. Med. Chem. 2014, 57, 3595–3611.
[
[
[
3] a) J. Magano, J. R. Dunetz, Chem. Rev. 2011, 111, 2177–
2
1
250; b) D. Y.-K. Chen, S. W. Youn, Chem. Eur. J. 2012,
8, 9452–9474.
4] Review: J. Atzrodt, V. Derdau, T. Fey, J. Zimmermann,
Angew. Chem. 2007, 119, 7890–7911; Angew. Chem. Int.
Ed. 2007, 46, 7744–7765.
5] Recent examples catalyzed by base metals, Al:
a) M. H. G. Prechtl, M. Teltewskoi, A. Dimitrov, E.
Kemnitz, T. Braun, Chem. Eur. J. 2011, 17, 14385–
14388; Fe: b) R. P. Yu, D. Hesk, N. Rivera, I. Pelczer,
P. J. Chirik, Nature 2016, 529, 195–199.
6] Recent examples catalyzed by precious metals, Ru:
a) M. H. G. Prechtl, M. Hçlscher, Y. Ben-David, N.
Theyssen, R. Loschen, D. Milstein, W. Leitner, Angew.
Chem. 2007, 119, 2319–2322; Angew. Chem. Int. Ed.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
[
12] Br/D exchange: a) H.-H. Zhang, P. V. Bonnesen, K.
Hong, Org. Chem. Front. 2015, 2, 1071–1075; b) M.
Janni, S. Peruncheralathan, Org. Biomol. Chem. 2016,
1
4, 3091–3097.
[
13] R. M. Bullock, Catalysis Without Precious Metals,
Wiley-VCH, Weinheim, 2010.
[
[14] Recent examples: a) S. Ge, J. F. Hartwig, Angew. Chem.
2012, 124, 13009–13013; Angew. Chem. Int. Ed. 2012, 51,
12837–12841; b) S. Z. Tasker, A. C. Gutierrez, T. F.
Jamison, Angew. Chem. 2014, 126, 1889–1892; Angew.
Chem. Int. Ed. 2014, 53, 1858–1861; c) A. Borzenko,
N. L. Rotta-Loria, P. M. MacQueen, C. M. Lavoie, R.
McDonald, M. Stradiotto, Angew. Chem. 2015, 127,
2
007, 46, 2269–2272; b) G. Pieters, C. Taglang, E.
Bonnefille, T. Gutmann, C. Puente, J.-C. Berthet, C.
Dugave, B. Chaudret, B. Rousseau, Angew. Chem. 2014,
1
26, 234–238; Angew. Chem. Int. Ed. 2014, 53, 230–234;
3
844–3848; Angew. Chem. Int. Ed. 2015, 54, 3773–3777;
Rh: c) S. K. Hanson, D. M. Heinekey, K. I. Goldberg,
Organometallics 2008, 27, 1454–1463; d) J. L. Rhinehart,
K. A. Manbeck, S. K. Buzak, G. M. Lippa, W. W.
Brennessel, K. I. Goldberg, W. D. Jones, Organometal-
lics 2012, 31, 1943–1952; Pd: e) V. Derdau, J. Atzrodt, J.
Zimmermann, C. Kroll, F. Brꢁckner, Chem. Eur. J.
2009, 15, 10397–10404; f) S. Ma, G. Villa, P. S. Thuy-
Boun, A. Homs, J.-Q. Yu, Angew. Chem. 2014, 126,
d) J. A. Fernꢄndez-Salas, E. Marelli, S. P. Nolan, Chem.
Sci. 2015, 6, 4973–4977; e) Z. Ruan, S. Lackner, L.
Ackermann, Angew. Chem. 2016, 128, 3205–3209;
Angew. Chem. Int. Ed. 2016, 55, 3153–3157; f) C. M.
Lavoie, P. M. MacQueen, N. L. Rotta-Loria, R. S.
Sawatzky, A. Borzenko, A. J. Chisholm, B. K. V. Har-
greaves, R. McDonald, M. J. Ferguson, M. Stradiotto,
Nat. Commum. 2016, 7, 11073–11083.
7
53–756; Angew. Chem. Int. Ed. 2014, 53, 734–737; Ir:
g) A. Azua, S. Sanz, E. Peris, Chem. Eur. J. 2011, 17,
963–3967; h) M. Parmentier, T. Hartung, A. Pfaltz, D.
[
15] Reviews: a) W. Keim, Angew. Chem. Int. Ed. 1990, 29,
2
35–244; b) S. Z. Tasker, E. A. Standley, T. F. Jamison,
3
Nature 2014, 509, 299–309.
Muri, Chem. Eur. J. 2014, 20, 11496–11504; i) W. J. Kerr,
M. Reid, T. Tuttle, ACS Catal. 2015, 5, 402–410; j) W. J.
Kerr, D. M. Lindsay, M. Reid, J. Atzrodt, V. Derdau, P.
Rojahn, R. Weck, Chem. Commun. 2016, 52, 6669–6672;
Pt: k) M. H. Emmert, J. B. Gary, J. M. Villalobos, M. S.
Sanford, Angew. Chem. 2010, 122, 6020–6022; Angew.
Chem. Int. Ed. 2010, 49, 5884–5886; l) Y. Sawama, T.
Yamada, Y. Yabe, K. Morita, K. Shibata, M. Shigetsura,
Y. Monguchi, H. Sajiki, Adv. Synth. Catal. 2013, 355,
1529–1534.
[
16] Reviews: a) V. B. Phapale, D. J. Cꢄrdenas, Chem. Soc.
Rev. 2009, 38, 1598–1607; b) R. Jana, T. P. Pathak, M. S.
Sigman, Chem. Rev. 2011, 111, 1417–1492; c) J. Yama-
guchi, K. Muto, K. Itami, Eur. J. Org. Chem. 2013, 19–
30; d) F.-S. Han, Chem. Soc. Rev. 2013, 42, 5270–5298;
e) J. Cornella, C. Zarate, R. Martin, Chem. Soc. Rev.
2
014, 43, 8081–8097; f) V. P. Ananikov, ACS Catal. 2015,
5
, 1964–1971.
[
17] Recent examples with aromatic substrates: a) C. Lohre,
T. Drçge, C. Wang, F. Glorius, Chem. Eur. J. 2011, 17,
[7] Review: F. Alonso, I. P. Beletskaya, M. Yus, Chem. Rev.
002, 102, 4009–4091.
6
052–6055; b) T. Fujihara, K. Nogi, T. Xu, J. Terao, Y.
2
Tsuji, J. Am. Chem. Soc. 2012, 134, 9106–9109; c) M. R.
Harris, L. E. Hanna, M. A. Greene, C. E. Moore, E. R.
Jarvo, J. Am. Chem. Soc. 2013, 135, 3303–3306; d) K.
Yang, C. Zhang, P. Wang, Y. Zhang, H. Ge, Chem. Eur.
J. 2014, 20, 7241–7244; e) A. M. Whittaker, V. M. Dong,
Angew. Chem. 2015, 127, 1328–1331; Angew. Chem. Int.
Ed. 2015, 54, 1312–1315; f) S.-Y. Yan, Y.-J. Liu, B. Liu,
Y.-H. Liu, B.-F. Shi, Chem. Commun. 2015, 51, 4069–
4072; g) J. Cornella, E. P. Jackson, R. Martin, Angew.
Chem. 2015, 127, 4147–4150; Angew. Chem. Int. Ed.
2015, 54, 4075–4078; h) M. Tobisu, T. Takahira, T.
Morioka, N. Chatani, J. Am. Chem. Soc. 2016, 138,
6711–6714.
[
8] a) V. A. Kallepalli, K. A. Gore, F. Shi, L. Sanchez, G. A.
Chotana, S. L. Miller, R. E. Maleczka, Jr., M. R. Smi-
th, III J. Org. Chem. 2015, 80, 8341–8353; b) G. Barker,
S. Webster, D. G. Johnson, R. Curley, M. Andrew, P. C.
Young, S. A. Macgregor, A.-L. Lee, J. Org. Chem. 2015,
8
0, 9807–9816.
9] a) S. Matsubara, Y. Yokota, K. Oshima, Org. Lett. 2004,
, 2071–2073; b) M. Rudzki, A. Alcalde-Aragonꢂs, W. I.
Dzik, N. Rodrꢃguez, L. J. Gooßen, Synthesis 2012, 44,
84–193; c) R. Grainger, A. Nikmal, J. Cornella, I.
Larrosa, Org. Biomol. Chem. 2012, 10, 3172–3174.
[
6
1
[10] a) J. D. Revell, A. Ganesan, Chem. Commun. 2004,
1916–1917; b) A. Mori, T. Mizusaki, T. Ikawa, T.
Adv. Synth. Catal. 2016, 358, 1–7
5
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
[18] a) K. W. Quasdorf, X. Tian, N. K. Garg, J. Am. Chem.
Soc. 2008, 130, 14422–14423; b) G, A. Molander, F.
Beaumard, Org. Lett. 2010, 12, 4022-4025; c) P. Y.
Yeung, C. M. So, C. P. Lau, F. Y. Kwong, Angew. Chem.
N. K. Garg, J. Am. Chem. Soc. 2011, 133, 6352–6363;
f) P. Leowanawat, N. Zhang, A.-M. Resmerita, B. M.
Rosen, V. Percec, J. Org. Chem. 2011, 76, 9946–9955;
g) G.-J. Chen, F.-S. Han, Eur. J. Org. Chem. 2012, 3575-
3579; h) P. Leowanawat, N. Zhang, V. Percec, J. Org.
Chem. 2012, 77, 1018-1025; i) G. A. Molander, I. Shin,
Org. Lett. 2013, 15, 2534–2537; j) T. Agrawal, S. P. Cook,
Org. Lett. 2014, 16, 5080–5083.
2
010, 122, 9102–9106; Angew. Chem. Int. Ed. 2010, 49,
8
918–8922; d) A. R. Ehle, Q. Zhou, M. P. Watson, Org.
Lett. 2012, 14, 1202–1205; e) R. Takise, K. Muto, J.
Yamaguchi, K. Itami, Angew. Chem. 2014, 126, 6909–
6
912; Angew. Chem. Int. Ed. 2014, 53, 6791–6794; f) X.
[
20] Reviews: a) B. M. Rosen, K. W. Quasdorf, D. A. Wilson,
N. Zhang, A.-M. Resmerita, N. K. Garg, V. Percec,
Chem. Rev. 2011, 111, 1346–1416; b) T. Mesganaw, N. K.
Garg, Org. Process Res. Dev. 2013, 17, 29–39.
21] M. Kuriyama, S. Matsuo, M. Shinozawa, O. Onomura,
Org. Lett. 2013, 15, 2716–2719.
Liu, C.-C. Hsiao, I. Kalvet, M. Leiendecker, L. Guo, F.
Schoenebeck, M. Rueping, Angew. Chem. 2016, 128,
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
6
918–6203; Angew. Chem. Int. Ed. 2016, 55, 6093–6098.
[19] a) K. W. Quasdorf, M. Riener, K. V. Petrova, N. K.
Garg, J. Am. Chem. Soc. 2009, 131, 17748–17749;
b) S. D. Ramgren, A. L. Silberstein, Y. Yang, N. K.
Garg, Angew. Chem. 2011, 123, 2219–2221; Angew.
Chem. Int. Ed. 2011, 50, 2171–2173; c) M. Baghbanza-
deh, C. Pilger, C. O. Kappe, J. Org. Chem. 2011, 76,
[
[
22] a) P. Leowanawat, N. Zhang, M. Safi, D. J. Hoffman,
M. C. Fryberger, A. George, V. Percec, J. Org. Chem.
2
012, 77, 2885–2892; b) R. L. Jezorek, N. Zhang, P.
Leowanawat, M. H. Bunner, N. Gutsche, A. K. R. Pesti,
J. T. Olsen, V. Percec, Org. Lett. 2014, 16, 6326–6329.
1
507–1510; d) L. Ackermann, R. Sandmann, W. Song,
Org. Lett. 2011, 13, 1784–1786; e) K. W. Quasdorf, A.
Antoft-Finch, P. Liu, A. L. Silberstein, A. Komaromi, T.
Blackburn, S. D. Ramgren, K. N. Houk, V. Snieckus,
[23] W. K. Chow, C. M. So, C. P. Lau, F. Y. Kwong, Org.
Chem. Front. 2014, 1, 464–467.
Adv. Synth. Catal. 2016, 358, 1–7
6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
UPDATES
Nickel-Catalyzed Deoxygenative Deuteration of Aryl
Sulfamates
Adv. Synth. Catal. 2016, 358, 1–7
M. Kuriyama*, S. Kujirada, K. Tsukuda, O. Onomura*
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5