Rhenium-catalyzed dehydrogenative olefination of C(sp3)-H bonds with hypervalent iodine(III) reagents

Article abstract of DOI:10.1039/c5ob00619h

A dehydrogenative olefination of C(sp³)-H bonds is disclosed here, by merging rhenium catalysis with an alanine-derived hypervalent iodine(iii) reagent. Thus, cyclic and acyclic ethers, toluene derivatives, cycloalkanes, and nitriles are all successfully alkenylated in a regio- and stereoselective manner.

Full text of DOI:10.1039/c5ob00619h

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DOI: 10.1039/C5OB00619H
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Rhenium‐Catalyzed Dehydrogenative Olefination of C(sp3)−H
Bonds with Hypervalent Iodine(III) Reagents
Received 00th January 20xx,
Accepted 00th January 20xx
Haidong Gu and Congyang Wang*
DOI: 10.1039/x0xx00000x
www.rsc.org/
A dehydrogenative olefination of C(sp3)−H bonds is disclosed here direct arylation of olefins by using Pd‐catalysts and diaryliodonium
by merging rhenium catalysis with an Alanine‐derived hypervalent salts, while Gaunt et al.10g demonstrated the Cu‐variant of these
iodine(III) reagent. Thus, cyclic and acyclic ethers, toluene reactions with wider substrate scopes (Scheme 1, a). Szabó and co‐
derivatives, cycloalkanes, and nitriles are all successfully workers11 disclosed the Pd‐catalyzed acyloxylation of alkenes with
alkenylated in a regio‐ and stereoselective manner.
carboxylic acid‐derived HIRs giving formally allylic C‐H bond
functionalized products (Scheme 1, b). Meanwhile, Buchwald,12a
Wang,12b Sodeoka,12c and Xiao et al.12d developed the Cu‐catalyzed
alkene trifluoromethylation reactions by employing Togni reagents
(Scheme 1, c). Afterwards, Li,13a Glorius,13b and Loh et al.13c reported
the Rh‐ and Ir‐catalyzed alkene alkynylation reactions with the aid
of alkynyl‐HIRs (Scheme 1, d). We have recently developed an
oxyalkylation reaction of olefins by merging rhenium catalysis with
carboxylic acid‐derived HIRs.8 As our continuous interests in the use
of Re‐catalysis14,15 and HIRs in organic synthesis, herein we disclose
a dehydrogenative olefination of C(sp3)‐H bonds by merging Re‐
catalysis with an Alanine‐derived HIR (Scheme 1, e).
Hypervalent iodine(III) reagents (HIRs) have wide applications in
organic synthesis because of their ready availability, easy handling,
varied reactivities, and benign environmental character.1 As a
prominent instance, HIRs have received considerable attention in
alkene difunctionalization reactions, which are of great importance
for chemical elaborations of complex molecules from simple olefin
feedstock.2 In general, HIRs play a dual role in metal‐free alkene
difunctionalization: as electrophiles to activate olefins thus
affording three‐membered iodonium ion intermediates and then as
good leaving groups towards attack of other nucleophiles. Though
successful, this mechanistic profile accounts for the limited reaction
types of alkene difunctionalizations promoted solely by HIRs.3 Since
2005, the merging of transition metal catalysis with HIRs has evoked
surging investigations on alkene difunctionalizations due to the
power and versatility of transition metal catalysts.4‐9 In these events,
HIRs are imparted a new function, that is, oxidation of transition
metal species from low oxidation states to high ones, which is
essential to achieve efficient catalytic turnovers for varied alkene
difunctionalization reactions. So far, the successful HIR‐enabled
redox couples in these transformations include PdII/PdIV,4 AuI/AuIII,5
CuI/CuIII,6 RuII/RuIII,7 IrIII/IrIV,7 ReI/ReII,8 and so on.9 As a result, the
control of reaction regio‐ and stereoselectivity as well as the
diversity of reaction categories has been largely improved.
In comparison with alkene difunctionalization, alkene
monofunctionalization, maintaining the olefin double bonds, has
been less studied through the combinatorial use of transition metal
catalysts and HIRs. Kang,10a‐b Ma,10c and others10d‐f described the
Scheme 1 Transition‐Metal‐Catalyzed Alkene Mono‐Functionalization Reactions with
HIRs.
Intrigued by synthetic transformations of cheap feedstock (such
as tetrahydrofuran and 1,4‐dioxane),16 we selected alkene 1d and
1,4‐dioxane 2a as model substrates to screen the reaction
conditions (Table 1).17 In the presence of 2.5 mol% Re2(CO)10, HIR
3a did promote the reaction to give the dehydrogenative
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of
Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of
Sciences, Beijing 100190, China. E‐mail: wangcy@iccas.ac.cn.
† Electronic Supplementary Information (ESI) available: Experimental details,
characterization data and NMR spectra for all new compounds. See
DOI: 10.1039/x0xx00000x
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a Reaction conditions: 1d (0.2 mmol), 3 (0.4 mmol), 1,4‐dioxane 2a (0.1 M), 120 oC,
olefination product 4da, albeit only in 12% yield with contaminant
formation of the oxymethylation product 5da (entry 1).8 The use of
HIR 3b, however, completely inhibited the expected reaction (entry
2).17 While no reaction occurred with N‐unprotected HIR 3c (entry
3), N‐methyl and –ethyl variants (3d and 3e) substantially increased
the yields of 4da (entries 4‐5). Further enhancement of the
bulkiness of N‐substituents (Bn, t‐Bu) gave comparable results
(entries 6‐7). Interestingly, HIR 3h, 3i, and 3j, derived from the
simple amino acid Glycine, β‐Alanine, and Alanine respectively,18
showcased promising reactivities with 3j being the best (entries 8‐
10). Presumably, the subtly tuned steric and electronic properties of
the N‐substituents might attribute to the stability and reactivity of
the N‐radical species (vide infra). Of note, the use of other oxidants
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3 h. b Determined by GC‐MS using mesitylene (0.1 mmol) as an internal standard.
DOI: 10.1039/C5OB00619H
c E‐isomer only. d No catalyst. e 3j (0.8 mmol), 1,4‐dioxane (0.05 M), 4 h. f Isolated
yield on 1.0 mmol scale. g 6j was isolated in 96 % yield.
Then, we commenced to investigate the scope of olefins
(Scheme 2). It was shown that styrene derivatives bearing both
electro‐donating and –withdrawing groups were tolerant in the
reaction (4aa‐ia).
2‐Vinylnaphthalene also delivered the
corresponding product 4ja smoothly. Meta‐ and ortho‐substituents
had no obvious effect on the reaction outcome (4ka‐ma).
Furthermore, 1,1‐diphenylethylene was also amenable to this
protocol giving the expected product 4na in good yield. It should be
pointed out that 1,2‐disubstituted olefins showed low reactivity in
this reaction presumably due to the steric hindrance in the step of
C‐C bond formation.17 Interestingly, the exocyclic olefin 1o reacted
with 1,4‐dioxane under the modified reaction conditions affording
the double‐bond migrated product 4oa and its oxidatively
aromatized product 4oa' (Scheme 3).
t
like BuOOH and (tBuO)2 instead of HIRs gave much worse results
under otherwise the same conditions.17 The control experiment
demonstrated that only a low yield of 4da was obtained in the
absence of Re2(CO)10 (entry 11). Remarkably, inferior results were
got by using other Re‐catalysts, Mn‐catalysts, and other transition
metal like Pd‐, Cu‐, and Fe‐catalysts as well as traditional Lewis acid
catalysts (entries 12‐17),17 which underlined the unique reactivity of
Re2(CO)10 in this reaction. Finally, 4da could be isolated in 66% yield
as a sole E‐isomer under the optimized reaction conditions (entry
18). Of note, 3j was reduced to 2‐iodobenzamide 6j in 96% isolated
yield, which can be easily oxidized by peracetic acid to regenerate
HIR 3j.17
Table 1 Screening of Reaction Parametersa
yields (%)b
entry
cat. (mol%)
HIRs
4dac
12
0
5da
19
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18e
Re2(CO)10 (2.5)
Re2(CO)10 (2.5)
Re2(CO)10 (2.5)
Re2(CO)10 (2.5)
Re2(CO)10 (2.5)
Re2(CO)10 (2.5)
Re2(CO)10 (2.5)
Re2(CO)10 (2.5)
Re2(CO)10 (2.5)
Re2(CO)10 (2.5)
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3j
3j
3j
0
15
53
46
55
48
64
73
24
18
10
0
Scheme 2 Scope of Olefins. Reaction conditions: 1 (1.0 mmol), 3j (4.0 mmol), Re2(CO)10
(2.5 mol%), 1,4‐dioxane (0.05 M), 120 oC, 4 h. Isolated yields of products 4 (%) are
shown. a Re2(CO)10 (5 mmol%), 1,4‐dioxane (0.03 M), 150 oC.
d
‐
Re(CO)5Br (5)
Mn2(CO)10 (5)
Pd(OAc)2 (5)
CuBr (5)
ZnCl2 (5)
Sc(OTf)3 (5)
Re2(CO)10 (2.5)
3j
3j
3j
3j
14
0
19
Scheme 3 Reaction of 1‐Methylene‐1,2,3,4‐tetrahydronaphthalene and 1,4‐Dioxane.
0
0
3j
84(66) f,g
Next, the compatibility of substrates bearing various C(sp3)‐H
bonds was tested with olefin 1n as the reaction partner (Table 2).
Alkyl ethers, no matter cyclic or acyclic, could deliver the expected
products successfully (entries 1‐2). Toluene, xylenes, and
mesitylene containing benzylic C‐H bonds were also smoothly
alkenylated to afford the corresponding products in good yields
(entries 3‐6). Functionalities like cyano and iodo groups were well
tolerant under the reaction conditions (entries 7‐8). Cyclic alkanes
OAc
OAc
R' = H, 3c
OCOCF3
I
OAc
I
CO2Me
I
I
R' = Me, 3d
R' = Et, 3e
R' = Bn, 3f
R' = t-Bu, 3g
N
R'
N
Ph
OCOCF3
Ph
OAc
3a
3b
CO2Me
3h
O
O
OAc
OAc
I
CO2Me
I
I
H
N
N
N
CO2Me
O
O
O
3j
3i
6j
2 | J. Name., 2012, 00, 1‐3
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such as cyclopentane, ‐hexane, and –ocatane were all suitable to form benzylic cation 13 and regenerate the catalytically active
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DOI: 10.1039/C5OB00619H
substrates giving the olefination products in good to excellent yields Re(n) species. It should be noted that 12 might also be oxidized by
(entries 9‐11). Furthermore, allylic nitrile 4nm could be easily HIR 3j, which constitutes an alternative but less competent pathway
obtained from the reaction of olefin 1n and acetonitrile in particularly when the rhenium catalyst is absent in the reaction
synthetically useful yield with the concurrent formation of N‐ (Table 1, entry 11). Finally, deprotonation of 13 leads to the final
olefination product 7j, originating from the reaction of 1n and Ala‐ formation of product 4.
HIR 3j (entry 12).
a) Trapping the C-radical formed via H-abstraction
Table 2 Scope of Substrates Bearing Various C(sp3)‐H Bondsa
5 mol% Re2(CO)10
Ala-HIR 3j
N
+
N
THF, 150 oC, 4 h
O
O
H
O
O
Ph
2b
1n
8:
TEMPO
(
)
31%
25%
Ph
1n
8:
no
yield
(%)b
yield
(%)b
b) Reaction of 1-phenylvinylcyclopropanewith 1,4-dioxane
entry
1
product 4
entry
7d
product 4
O
O
O
5 mol% Re2(CO)10
O
O
Ala-HIR 3j
4nb:
88
4nh:
69
O
H
+
+
1,4-dioxane
120 oC, 4 h
H
4nc:
50
4ni:
61
2c
3
8d
9e
1p
2a
34% (4oa:4oa' = 6.3:1)
radical addition
O
O
O
[O], - H
O
O
4nd:
62
4nj:
91
O
rearrangement
cyclization
4ne:
64
4nk:
95
4d
5d
10e
11e
H
Scheme 4 Mechanistic Experiments.
4nf:
67
4nl:
71
4ng:
66
4nm:
58
6
12f
a Reaction conditions: 1n (1.0 mmol), 3j (4.0 mmol), Re2(CO)10 (5 mol%), 2 (0.03
M), 150 oC, 4 h. b Isolated yields of products 4. c Re2(CO)10 (2.5 mmol%), Et2O
(0.05 M), 120 oC. d 2 (0.2 M). e 2 (0.1 M), 12 h. f 7j was isolated in 11% yield.
We assumed that the initial C(sp3)‐H activation occur through a
radical H‐abstraction pathway. In order to verify this hypothesis, the
radical‐trapping reagent TEMPO was subjected to the reaction
conditions of olefin 1n and tetrahydrofuran 2b (Scheme 4, a). To
our delight, the α‐THF radical trapped product 8 was isolated in 31%
yield and the olefination reaction was completely prohibited, which
confirmed our assumption. Also, compound 8 could be obtained in
comparable yield in the absence of 1n. Next, the reaction of 1‐
phenylvinylcyclopropane 1p, susceptible to radical rearrangements,
and 1,4‐dioxane 2a was carried out (Scheme 4, b). It turned out that
the ring expansion product 4oa and its aromatized product 4oa'
were formed in 34% yield. This result supported a reaction
sequence of radical addition/rearrangement/cyclization/oxidative
deprotonation.19
Scheme 5 A Tentative Reaction Mechanism.
In conclusion, the dehydrogenative olefination of C(sp3)‐H
bonds was developed through the combination of rhenium‐
catalysis and an Alanine‐derived hypervalent iodine(III)
reagents, which demonstrates a reactivity quite distinct from
known combinations of transition metal catalysts and
hypervalent iodine(III) reagents. Also, this reaction represents
a rare example in organic synthesis where amino acid‐derived
HIRs play a unique role since they were synthesized by
Zhdankin et al.18 Thus, cheap and easily available feedstock
such as cyclic and acyclic ethers, toluene derivatives,
cycloalkanes, and nitriles could all be successfully alkenylated
in a regio‐ and stereoselective way.20 Mechanistic studies
revealed a radical‐initiated pathway operating in the reaction.
Based on the above observations,
a tentative reaction
mechanism was proposed in Scheme 5. Heterolytic cleavage of the
I‐O bond in HIR 3j gives rise to the ionic species 9, which undergoes
a single electron transfer process with the Re(n) catalyst affording
N‐radical species 10. The H‐atom α to oxygen in 1,4‐dioxane is
abstracted by 10 giving rise to the α‐C radical species 11 and 2‐
iodobenzamide 6j. The ensuing radical addition of 11 to olefin
affords benzylic radical 12, which is oxidized by the Re(n+1) species
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52, 9781; (h) F. Wang, X. Qi, Z. Liang, P. CheVniewanAdrticGle.OnLliinue,
Angew.Chem., Int. Ed., 2014, 53, 1881D. OI: 10.1039/C5OB00619H
Ru‐ or Ir‐catalysis with HIRs, see: (a) J. Xie, P. Xu, H. Li, Q. Xue,
H. Jin, Y. Cheng and C. Zhu, Chem. Commun., 2013, 49, 5672;
(b) P. Xu, J. Xie, Q. Xue, C. Pan, Y. Cheng and C. Zhu, Chem.
Eur. J., 2013, 19, 14039; (c) G. Fumagalli, S. Boyd and M. F.
Greaney, Org. Lett., 2013, 15, 4398.
Further exploitations on merging rhenium‐catalysis with
hypervalent iodine(III) reagents in organic synthesis are
underway in our laboratory.
Financial support from the National Basic Research
Program of China (973 Program) (No. 2011CB808600) and the
National Natural Science Foundation of China (21322203,
21272238, 21472194) are gratefully acknowledged.
7
8
9
Re‐catalysis with HIRs, see: Y. Wang, L. Zhang, Y. Yang, P.
Zhang, Z. Du and C. Wang, J. Am. Chem. Soc., 2013, 135
18048.
,
Fe‐catalysis with HIRs, see: H. Egami, R. Shimizu, Y. Usui and
M. Sodeoka, Chem. Commun., 2013, 49, 7346.
Notes and references
10 (a) S.‐K. Kang, K.‐Y. Jung, C.‐H. Park and S.‐B. Jang,
Tetrahedron Lett., 1995, 36, 8047; (b) S.‐K. Kang, H.‐W. Lee,
1
For general reviews: (a) T. Wirth, Angew. Chem., Int. Ed.,
2005, 44, 3656; (b) N. R. Deprez and M. S. Sanford, Inorg.
Chem., 2007, 46, 1924; (c) V. V. Zhdankin and P. J. Stang,
Chem. Rev., 2008, 108, 5299; (d) E. A. Merritt and B. Olofsson,
Angew. Chem., Int. Ed., 2009, 48, 9052.
S.‐B. Jang, T.‐H. Kim and S.‐J. Pyun, J. Org. Chem., 1996, 61
,
2604; (c) Y. Liang, S. Luo, C. Liu, X. Wu and Y. Ma,
Tetrahedron, 2000, 56, 2961; (d) A. Kina, H. Miki, Y.‐H. Cho
and T. Hayashi, Adv. Synth. Catal., 2004, 346, 1728; (e) J.
Aydin, J. M. Larsson, N. Selander and K. J. Szabó, Org. Lett.,
2009, 11, 2852; (f) B. R. Vaddula, A. Saha, J. Leazer and R. S.
Varma, Green Chem., 2012, 14, 2133; (g) R. J. Phipps, L.
McMurray, S. Ritter, H. A. Duong and M. J. Gaunt, J. Am.
Chem. Soc., 2012, 134, 10773.
2
For leading reviews on alkene difunctionalizations: (a) A.
Minatti and K. Muñiz, Chem. Soc. Rev., 2007, 36, 1142; (b) S.
R. Chemler and P. H. Fuller, Chem. Soc. Rev., 2007, 36, 1153;
(c) K. H. Jensen and M. S. Sigman, Org. Biomol. Chem., 2008,
6
, 4083; (d) J. P. Wolfe, Synlett, 2008, 2913; (e) R. I.
McDonald, G. Liu and S. S. Stahl, Chem. Rev., 2011, 111, 2981;
(f) S. E. Denmark, W. E. Kuester and M. T. Burk, Angew.
Chem., Int. Ed., 2012, 51, 10938; (g) W. Wu and H. Jiang, Acc.
Chem. Res., 2012, 45, 1736.
11 (a) L. T. Pilarski, N. Selander, D. Böse and K. J. Szabó, Org.
Lett., 2009, 11, 5518; (b) R. Alam, L. T. Pilarski, E. Pershagen
and K. J. Szabó, J. Am. Chem. Soc., 2012, 134, 8778.
12 (a) A. T. Parsons and S. L. Buchwald, Angew. Chem., Int. Ed.,
2011, 50, 9120; (b) X. Wang, Y. Ye, S. Zhang, J. Feng, Y. Xu, Y.
Zhang and J. Wang, J. Am. Chem. Soc., 2011, 133, 16410; (c)
R. Shimizu, H. Egami, Y. Hamashima and M. Sodeoka, Angew.
Chem., Int. Ed., 2012, 51, 4577; (d) X.‐P. Wang, J.‐H. Lin, C.‐P.
3
For recent examples: (a) H. M. Lovick and F. E. Michael, J. Am.
Chem. Soc., 2010, 132, 1249; (b) M. Fujita, Y. Yoshida, K.
Miyata, A. Wakisaka and T. Sugimura, Angew. Chem., Int. Ed.,
2010, 49, 7068; (c) C. R
ӧben, J. A. Souto, Y. González, A.
Lishchynskyi and K. Muñiz, Angew. Chem., Int. Ed., 2011, 50
,
Zhang, J.‐C. Xiao and X. Zheng Beilstein J. Org. Chem., 2013, 9,
2635. For a related process, see: (e) J. Xu, Y. Fu, D.‐F. Luo, Y.‐
Y. Jiang, B. Xiao, Z.‐J. Liu, T.‐J. Gong and L. Liu, J. Am. Chem.
9478; (d) Y.‐B. Kang and L. H. Gade, J. Am. Chem. Soc., 2011,
133, 3658; (e) Y. Li and A. Studer, Angew. Chem., Int. Ed.,
2012, 51, 8221; (f) U. Farid, F. Malmedy, R. Claveau, L. Albers
Soc., 2011, 133
,
15300. For
a
decarboxylative
and T. Wirth, Angew. Chem., Int. Ed., 2013, 52, 7018; (g) W.
difluoromethylation, see: (f) Z. He, M. Hu, T. Luo, L. Li and J.
Kong, P. Feige, T. de Haro and C. Nevado, Angew. Chem., Int.
Ed., 2013, 52, 2469.
Hu, Angew. Chem., Int. Ed., 2012, 51, 11545.
13 (a) F. Xie, Z. Qi, S. Yu and X. Li, J. Am. Chem. Soc., 2014, 136
,
4
Pd‐catalysis with HIRs, for selected examples: (a) E. J.
Alexanian, C. Lee and E. J. Sorensen, J. Am. Chem. Soc., 2005,
127, 7690; (b) J. Streuff, C. H. Hӧvelmann, M. Nieger and K.
4780; (b) K. D. Collins, F. Lied and F. Glorius, Chem. Commun.,
2014, 50, 4459; (c) C. Feng, D. Feng and T.‐P. Loh, Chem.
Commun., 2014, 50, 9865.
Muñiz, J. Am. Chem. Soc., 2005, 127, 14586; (c) G. Liu and S.
14 Y. Kuninobu and K. Takai, Chem. Rev., 2011, 111, 1938.
15 (a) D. Xia, Y. Wang, Z. Du, Q.‐Y. Zheng and C. Wang, Org. Lett.,
2012, 14, 588; (b) Q. Tang, D. Xia, X. Jin, Q. Zhang, X.‐Q. Sun
and C. Wang, J. Am. Chem. Soc., 2013, 135, 4628; (c) G. Mao,
B. Jia and C. Wang, Chin. J. Org. Chem. 2015, 35, 284.
16 R. He, X. Jin, H. Chen, Z.‐T. Huang, Q.‐Y. Zheng and C. Wang, J.
Am. Chem. Soc., 2014, 136, 6558.
S. Stahl, J. Am. Chem. Soc., 2006, 128, 7179; (d) L. V. Desai
and M. S. Sanford, Angew. Chem., Int. Ed., 2007, 46, 5737; (e)
Y. Li, D. Song and V. M. Dong, J. Am. Chem. Soc., 2008, 130
,
2962; (f) T. Wu, G. Yin and G. Liu, J. Am. Chem. Soc., 2009,
131, 16354; (g) S. Jaegil, J. Dufour, H. Wei, T. Piou, X.‐H. Duan,
J.‐P. Vors, L. Neuville and J. Zhu, Org. Lett., 2010, 12, 4498; (h)
S. Cui, L. Wojtas and J. C. Antilla, Angew. Chem., Int. Ed.,
2011, 50, 8927; (i) S. Nicolai, C. Piemontesi and J. Waser,
Angew. Chem., Int. Ed., 2011, 50, 4680.
17 For more details, see Supporting Information.
18 (a) V. V. Zhdankin, A. E. Koposov, J. T. Smart, R. R. Tykwinski,
R. McDonald and A. Morales‐Izquierdo, J. Am. Chem. Soc.,
2001, 123, 4095; (b) V. V. Zhdankin, A. Y. Koposov, L. S. Su, V.
V. Boyarskikh, B. C. Netzel and V. G. Young, Org. Lett., 2003,
5
6
Au‐catalysis with HIRs, see: (a) A. Iglesias and K. Muñiz, Chem.
Eur. J., 2009, 15, 10563; (b) T. de Haro and C. Nevado, Angew.
Chem. Int. Ed., 2011, 50, 906; (c) L. T. Ball, G. C. Lloyd‐Jones
and C. A. Russell, Chem. Eur. J., 2012, 18, 2931; (d) M. N.
Hopkinson, B. Sahoo and F. Glorius, Adv. Synth. Catal., 2014,
356, 2794.
Cu‐catalysis with HIRs, for selected examples: (a) R. Zhu and
S. L. Buchwald, J. Am. Chem. Soc., 2012, 134, 12462; (b) P. G.
Janson, I. Ghoneim, N. O. Ilchenko and K. J. Szabó, Org. Lett.,
2012, 14, 2882; (c) E. Cahard, N. Bremeyer and M. J. Gaunt,
Angew. Chem., Int. Ed., 2013, 52, 9284; (d) W. Kong, M.
Casimiro, E. Merino and C. Nevado, J. Am. Chem. Soc., 2013,
135, 14480; (e) H. Egami, R. Shimizu, S. Kawamura and M.
Sodeoka, Angew. Chem., Int. Ed., 2013, 52, 4000; (f) X. Liu, F.
Xiong, X. Huang, L. Xu, P. Li and X. Wu, Angew. Chem., Int.
Ed., 2013, 52, 6962; (g) Z.‐M. Chen, W. Bai, S.‐H. Wang, B.‐M.
Yang, Y.‐Q. Tu and F.‐M. Zhang, Angew. Chem., Int. Ed., 2013,
5
, 1583.
19 (a) T. W. Liwosz and S. R. Chemler, Chem. Eur. J., 2013, 19
,
12771; (b) T. W. Liwosz and S. R. Chemler, Org. Lett., 2013,
15, 3034; (c) B. Gao, Y. Zhao and J. Hu, Angew. Chem. Int. Ed.,
2015, 54, 638.
20 So far, there are only two reports on dehydrogenative
olefination of C(sp3)‐H bonds, albeit with limited types of
substrates. For ethers only: (a) D. Liu, C. Liu, H. Li and A. Lei,
Chem. Commun., 2014, 50, 3623. For cycloalkanes only: (b) Y.
Zhu and Y. Wei, Chem. Sci., 2014,
5, 2379. For related
reviews: (c) S. Tang, K. Liu, C. Liu and A. Lei, Chem. Soc. Rev.,
2015, 44, 1070; (d) C. Li, Acc. Chem. Res., 2009, 42, 335; (e)
S.‐Y. Zhang, F.‐M. Zhang, Y.‐Q. Tu, Chem. Soc. Rev., 2011, 40
,
1937.
4 | J. Name., 2012, 00, 1‐3
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