Rhodium(III)-Catalyzed Coupling of Arenes with Cyclopropanols via C-H Activation and Ring Opening

Article abstract of DOI:10.1021/acscatal.5b02414

Rhodium-catalyzed C-H activation of arenes has been established as an important strategy for the rapid construction of new bonds. On the other hand, ring-opening of readily available cyclopropanols has served as a driving force for the coupling with vario

Full text of DOI:10.1021/acscatal.5b02414

Subscriber access provided by University of Pennsylvania Libraries
Letter
Rhodium(III)-Catalyzed Coupling of Arenes with
Cyclopropanols via C-H Activation and Ring Opening
Xukai Zhou, Songjie Yu, Lingheng Kong, and Xingwei Li
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.5b02414 • Publication Date (Web): 21 Dec 2015
Downloaded from http://pubs.acs.org on December 25, 2015
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
ACS Catalysis is published by the American Chemical Society. 1155 Sixteenth Street
N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 5
ACS Catalysis
1
2
3
4
5
6
7
8
9
Rhodium(III)-Catalyzed Coupling of Arenes with Cyclopropanols via
C-H Activation and Ring Opening
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Xukai Zhou, Songjie Yu, Lingheng Kong, Xingwei Li*
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
ABSTRACT: Rhodium-catalyzed C-H activation of arenes has been established as an important strategy for the rapid
construction of new bonds. On the other hand, ring-opening of readily available cyclopropanols has served as a driving
force for the coupling with various nucleophiles and electrophiles. Nevertheless, these two important areas evolved
separately, and coupling of arenes with cyclopropanols via C-H activation has been rarely explored. In this work, the
oxidative coupling between arenes and cyclopropanols has been realized with high efficiency and selectivity under
Rh(III)-catalysis, providing an efficient route to access β-aryl ketones. Moreover, the C-H bond has been extended to
benzylic C-H bonds.
KEYWORDS : rhodium(III) catalysis, C-H activation, strained ring, ring opening, cyclopropanols
Modern synthetic organic chemistry benefits
tremendously from advances in strained ring opening
reactions.1 In recent years the chemistry of strain rings,
and particularly three-membered rings, has been
extensively investigated.2 Cyclopropanols are readily
available three-membered rings that have been found
wide applications in organic synthesis and in many
natural products.3 Driven by the strain, metal-catalyzed
and metal-free ring-opening of cyclopropanols has been
challenge whether the mandatory oxidative conditions
can be compatible with the C-H activation and the
ring-opening processes. Significantly, this coupling
process would generate a synthetically important
β-aryl
ketone. We noted that while the -aryl ketone product
β
could be obtained in several cases via Rh(III)-catalyzed
hydroarylation of olefins,9 the reports are very limited
because in most systems β-H elimination is predominant,
leading to oxidative olefination.10
well-known,4
especially
in
metal-catalyzed
ring-opening-coupling with both electrophiles and
nucleophiles,5 leading to formation of various types of
C-C bonds. Nevertheless, all these synthetic methods
required a pre-functionalized coupling partner.
On the other hand, metal-catalyzed C-H activation has
emerged as an efficient and step- and atom-economic
strategy for C-C bond formation.6 Among the numerous
transition metals, rhodium(III) catalysis have significantly
contributed to the arsenal of new bond formation.7
Despite the significance of both C-H activation and ring
opening of cyclopropanols, these two important areas
evolved nearly separately. To our knowledge, only one
Scheme 1. Combination of C-H activation with
ring-opening of cyclopronanols
We initiated our studies with the coupling between
oxime ether 1a and 1-benzylcyclopropanol (2a, Table 1).
When 1a and 2a were treated with [Cp*RhCl2]2 (4 mol %),
report
documented
the
tandem
cyclopropanol
rearrangement with intramolecular C-H activation to
yield 1-indanones (scheme 1a).5d On the other hand,
although several systems of Rh(III)-catalyzed C-H
activation of arenes and coupling other three-membered
rings have been reported, they all occurred under
redox-neutral conditions.8 We reasoned that Rh(III)
catalysts may play a dual role in both C-H activation and
in the ring-opening of cyclopropanols. However, given the
nucleophilic nature of cyclopropanol, it remains a big
.
CsOAc (25 mol %), and Cu(OAc)2 H2O oxidant in
methanol (100 oC), the desired product 3aa was isolated in
only 27% yield (entry 1). The replacement of CsOAc with
AgSbF6 as an additive only resulted in lower yield (entry
2). Using [Cp*Rh(OAc)2] as a catalyst also led to lower
yield (entry 3). Effects of the reaction temperature were
then examined, and coupling at 40 oC or a higher
temperature all gave inferior results (entry 4-5, 7-8). Thus,
ACS Paragon Plus Environment

ACS Catalysis
Page 2 of 5
the optimal efficiency was reached when the reaction was cases, the reaction proceeded with high regio-selectivity
1
2
3
performed at rt. Screening also revealed that other
common solvents such as DCE, MeCN, and toluene are
not viable.
and high mono-/di- selectivity. Furthermore, essentially
no enone byproduct via overoxidation of the saturated
ketone was observed.
4
5
Table 1. Optimization Studiesa
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
entry
1
catalyst
temp (oC)
100
yield (%)b
27
[Cp*RhCl2]2
2c
3d
4
[Cp*RhCl2]2
[Cp*Rh(OAc)2]
[Cp*RhCl2]2
100
100
80
9
20
33
5
[Cp*RhCl2]2
60
42
6e
7
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
60
40
42
64
70
75
75
Scheme 2. Substrate Scope of Oximes.a,b aReactions were
carried out using [Cp*RhCl2]2 (4 mol %), CsOAc (25 mol
%), Cu(OAc)2 H2O (2.1 equiv), 1 (0.2 mmol), and 2a (0.25
mmol) in a MeOH (2 mL) at room temperature for 16 h.
bIsolated yield after column chromatography.
.
8
RT
RT
RT
9f
10g
Encouraged by these initial findings, we sought to
further define the scope of this coupling reaction using
other arenes. It was found that N-pyrimidinylindoles
could serve as a viable substrate.11 Through extensive
optimization of the reaction conditions in the coupling of
indole 4a and 2a (See Table S1 in the SI), the product 6aa
was obtained in 83% yield under the following reaction
conditions: [Cp*Rh(OAc)2] (2 mol %), PhCO2H (25 mol
a Reactions were carried out using [Cp*Rh(Cl)2]2 (4 mol
%), CsOAc (25 mol %), Cu(OAc)2 H2O (2.1 equiv), 4a (0.2
.
b
mmol), and 2a (0.25 mmol) in a solvent (2 mL) for 12 h.
Isolated yield after column chromatography. c AgSbF6 (16
mol %) instead of CsOAc (25 mol %). d [Cp*Rh(OAc)2] (8
mol %) was used with no additive. e CsOPiv instead of
%), and Cu(OAc)2 H2O in MeOH (100 oC, 24 h). The
.
f
g
CsOAc. The reaction was performed for 16 h. The
reaction was performed for 20 h.
benzoic acid additive likely facilitated C-H activation of
the arene as in
a
CMD mechanism.12 While
N-pyrimidinylindoles can be highly efficient in many
With the optimal conditions in hand, we next examined
the scope and generality of this coupling system (Scheme
2). Various para substituted O-methyl oximes readily
coupled with 2a under the standard conditions to afford
the products in 60%-80% yield (3ba-3fa). Meanwhile,
electron-donating groups tends to enhance the efficiency
(3ea, 3ia), and electron-withdrawings or halogen groups
at the para and meta positions of the benzene ring led to
lower yields (3ba, 3fa, and 3ha). Moreover, the imine
substrate is not limited to acetophenone imines, and the
reaction yield was comparably high when the carbon
chain in the imine moiety was elongated or when a benzyl
substituent was introduced to the α-position (3ja, 3ka,
and 3la). However, the reaction yield was poor when the
substrate is conformationally rigid or sterically bulky
Rh(III)-catalyzed C-H activation systems, the reaction
o
needed to be performed at 100 C, but only a low loading
of the catalyst was necessary. With the establishment of
these
optimum
conditions,
the
scope
of
N-pyrimidinylindole was first evaluated (Scheme 3).
Generally, introduction of both electron-donating (6da,
6fa, 6ha) and –withdrawing (6ea, 6ia, 6ja) substituents
into different positions of the benzene ring was well
tolerated, and the reaction efficiency was marginally
affected by such electronic perturbation. Furthermore,
the reaction efficiency was essentially not affected when a
7-ethyl or a 3-methyl group was introduced, indicating
that the reaction tolerated steric effects at these two
positions.
(3ma
1-phenyl-substituted
O-methyl oximes afford 3af and 3ak in 35% yield. In all
and
3aj).
Furthermore,
cyclopropanol
1-ethyl-
coupled
and
with
ACS Paragon Plus Environment

Page 3 of 5
ACS Catalysis
1
2
3
4
5
6
7
8
9
Derivatization reactions have been carried out to
demonstrate the synthetic utility. In an attempt to
remove the pyrimidyl DG (eq 2), the expected NH indole
was not observed. Surprisingly, while the product (10) is
an NH indole as established unambiguously by X-ray
crystallography, the pyrimidyl group was retained with a
formal 1,4-shift (see SI for proposed mechanism). In
another experiment, treatment of 3aa with copper
powder in HCl/dioxane led to an indene product 11 in
high yield (eq 3).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Scheme 3. Substrate Scope of N-Pyrimidinylindoles.a,b
aReactions were carried out using [Cp*Rh(OAc)2](2 mol
%), PhCO2H (25 mol %), Cu(OAc)2.H2O (2.1 equiv), 4 (0.2
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The mechanism of C-H activation/coupling of oxime
ether 1a has been explored (Scheme 4). To gain insights
into the C-H activation process, kinetic isotope effect has
been measured from parallel experiments under identical
conditions using 1a and 1a-d5 with 2a being a coupling
partner (Scheme 4a). A value of kH/kD = 7.8 was obtained
on the basis of two rate constants. This large value
indicated that C-H bond cleavage is likely involved in the
turnover-limiting step.
o
mmol), and 2a (0.4 mmol) in MeOH (2 mL) at 100 C for
24 h. bIsolated yield after column chromatography.
The scope of the cyclopropanol substrate was then
examined.
In
general,
various
para-substituted
1-benzylcyclopropanols all underwent smooth coupling
with N-pyrimidinylindole (4a) under the standard
conditions to afford the ketone products in 59%-78%
yields
(6ab,
6ac,
6ad).
Furthermore,
meta-bromo-substituted 1-benzylcyclopronanol coupled
with comparably high efficiency (6ae). The substituent in
the cyclopronanol ring is not limited to a benzyl group,
and
alkyl,
cyclopropyl,
and
phenyl-substituted
cyclopropanols are also viable albeit with slightly lower
yield (6af, 6ag, and 6ak), where the reduced yield seems
to result from the formation of a detectable amount of
corresponding
high isolated yield was secured for the product 6ah which
originated from the coupling using
1-phenoxmethylcyclopronal. Interestingly, natural
α,β-unsaturated ketone. To our delight, a
a
a
product-derived cyclopropanol also exhibited activity,
albeit with 27 % yield.
Additional experiments have been carried out to move
beyond the activation of arene C-H bonds.
8-Methylquinolines
coupled
smoothly
with
1-benzylcyclopropanol to deliver the
γ
-aryl ketone
products in good yields (eq 1).13 This reaction represents
the first example of coupling of benzylic C-H bond with a
strained ring, leading to C(sp3)-C(sp3) formation.
Scheme 4. Mechanistic Studies
ACS Paragon Plus Environment

ACS Catalysis
Page 4 of 5
The detection of a small amount of enone byproducts
in some cases suggests the involvement of -H
elimination of III may also lead to 3aa (pathway (b)), we
1
2
3
4
5
6
7
8
reason that this is less likely because both oxime 1m (in
the coupling with 2a) and cyclopropanol 2j (in the
coupling with 1a) should be expected to react with
comparable reactivity in this pathway, while poor
reactivity for 2j would be expected in pathway (a) because
access to a Rh(III) tertiary alkyl via migratory insertion is
unlikely.
β
elimination and olefin species. Thus, several experiments
have been performed to probe this process. When the
coupling of 1a and 2a was performed in the presence of
ethyl vinyl ketone (EVK, 0.5 equiv), GC analysis revealed
the incorporation of EVK (Scheme 4b), indicating that
olefin species and accordingly a β-H elimination process
should be pertinent. This conclusion is also consistent
with the fact that H/D exchange was achieved at the one
of the alpha positions in product 3af,14 where CD3OD may
provide D to lead to a Rh-D species that undergoes
In summary, we have achieved the first combination of
C-H bond activation with ring opening of cyclopropanols
under Rh(III)-catalysis, furnishing an efficient route to
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
access
β-aryl ketones. The reaction may proceed under
reversible
β-D elimination (Scheme 4c). To probe the
mild conditions with broad scope, high regioselectivity,
and good functional group tolerance. Both oxime ethers
and N-pyrimidylindoles proved to be viable arene
substrates. Furthermore, this coupling system has been
extended to the activation of benzylic C-H bonds. This
work broadened the scope of strained rings in C-H
activation chemistry, and future studies are directed to
the C-H activation and ring opening-coupling with other
less reactive rings.
stage or sequence of olefin formation, 1a was allowed to
couple directly with EVK (Scheme 4d). However, only
traces of the hydroarylation product was detected with or
without Cu(OAc)2 (Scheme 4d). This suggests that
participation of cyclopropanol in the form of an enone via
initial oxidative opening prior to cyclometalation is
unlikely.
ASSOCIATED CONTENT
Supporting Information.
1
General experimental procedures, characterization data, H
and 13C NMR spectra of some starting materials and new
products (PDF), and X-ray crystallographic data of
compound 10 (CIF). This information is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*xwli@dicp.ac.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
Financial support from the NSFC (Nos. 21525208 and
21272231) is gratefully acknowledged.
Scheme 5. Proposed catalytic cycle.
On the basis of our results and previous reports,5g,15
a
REFERENCES
plausible mechanism is given in Scheme 5. Starting from
[Cp*Rh(OAc)2], cyclorhodation of substrate 1a forms a
rhodacycle I, and ligand exchange with a cyclopropanol
affords alkoxide II which subsequently undergoes
β-carbon elimination to produce a Rh(III) alky species
III.8a,8e-g β-hydride elimination of III should reversibly
occur to provide Rh(III) hydride IV with dissociation of
the imine chelator (pathway (a)). This proposal is in good
agreement with the inactivity of oxime ether 1m (product
3ma) because the rigidity enforced by the extra fused
cyclohexanone ring should disfavor imine dechelation.
Migratory insertion of the aryl into the olefin of IV
followed by C-H reductive elimination (or protonolysis)
of V furnished product 3aa together with a Rh(I), which is
oxidized by Cu(II) to regenerate the active Rh(III)
catalyst. Although an alternative direct C-C reductive
(1) (a) Rayabarapu, D. K.; Cheng, C.-H. Acc. Chem. Res. 2007,
40, 971-983. (b) Bournaud, C.; Chung, F.; Luna, A. P.; Pasco, M.;
Errasti, G.; Lecourt, T.; Micouin, L. Synthesis 2009, 41, 869-887.
(c) Seiser, T.; Saget, T.; Tran, D. N.; Cramer, N. Angew. Chem.,
Int. Ed. 2011, 50, 7740-7752. (d) Couty, F.; Drouillat, B.; Evano, G.;
David, O. Eur. J. Org. Chem. 2013, 2013, 2045-2056. (e) Rotstein,
B. H.; Zaretsky, S.; Rai, V.; Yudin, A. K. Chem. Rev. 2014, 114,
8323-8359. (f) Walczak, M. A. A.; Krainz, T.; Wipf, P. Acc. Chem.
Res. 2015, 48, 1149-1158. (g) Zhang, S.; Zhang, W.-X.; Xi, Z. Acc.
Chem. Res. 2015, 48, 1823-1831.
(2) (a) Rubin, M.; Rubina, M.; Gevorgyan, V. Chem. Rev. 2007,
107, 3117-3179. (b) Zhu, Z.-B.; Wei, Y.; Shi, M. Chem. Soc. Rev.
2011, 40, 5534-5563. (c) Shi, M.; Lu, J.-M.; Wei, Y.; Shao, L.-X.
Acc. Chem. Res. 2012, 45, 641-652. (d) Zhang, D.-H.; Tang, X.-Y.;
Shi, M. Acc. Chem. Res. 2014, 47, 913-924. (e) Marek, I.; Masarwa,
A.; Delaye, P.-O.; Leibeling, M. Angew. Chem., Int. Ed. 2015, 54,
ACS Paragon Plus Environment

Page 5 of 5
ACS Catalysis
414-429. (f) Archambeau, A.; Miege, F.; Meyer, C.; Cossy, J. Acc.
(8) (a) Cui, S.; Zhang, Y.; Wu, Q. Chem. Sci. 2013, 4, 3421-3426.
1
2
3
4
5
6
7
8
Chem. Res. 2015, 48, 1021-1031.
(b) Li, X.; Yu, S.; Wang, F.; Wan, B.; Yu, X. Angew. Chem., Int. Ed.
2013, 52, 2577-2580. (c) Hyster, T. K.; Rovis, T. Synlett 2013, 24,
1842-1844. (d) Yu, S.; Li, X. Org. Lett. 2014, 16, 1200-1203. (e)
Zhang, H.; Wang, K.; Wang, B.; Yi, H.; Hu, F.; Li, C.; Zhang, Y.;
Wang, J. Angew. Chem., Int. Ed. 2014, 53, 13234-13238. (f) Yu, S.;
Li, X. Org. Lett. 2014, 16, 1220-1223. (g) Wu, J.-Q.; Qiu, Z.-P.;
Zhang, S.-S.; Liu, J.-G.; Lao, Y.-X.; Gu, L.-Q.; Huang, Z.-S.; Li, J.;
Wang, H. Chem. Commun. 2015, 51, 77-80. Two leading examples
for palladium catalysis: (h) Du, H.; Yuan, W.; Zhao, B.; Shi, Y. J.
Am. Chem. Soc. 2007, 129, 7496-7497. (i) Peng, X.; Zhu, Y.;
Ramirez, T. A.; Zhao, B.; Shi, Y. Org. Lett. 2011, 13, 5244-5247.
(9) (a) Shi, Z.; Boultadakis-Arapinis, M.; Glorius, F. Chem.
Commun. 2013, 49, 6489-6491. (b) Huang, L.; Wang, Q.; Qi, J.;
Wu, X.; Huang, K.; Jiang, H. Chem. Sci. 2013, 4, 2665-2669. (c)
Lu, P.; Feng, C.; Loh, T.-P. Org. Lett. 2015, 17, 3210-3213. (d) Yang,
L.; Qian, B.; Huang, H. Chem. Eur. J. 2012, 18, 9511-9515. (e) Yang,
L.; Correia, C. A.; Li, C.-J. Org. Biomol. Chem. 2011, 9, 7176-7179.
(10) Kim, J.; Park, S.-W.; Baik, M.-H.; Chang, S. J. Am. Chem.
Soc. 2015, 137, 13448-13451.
(11) (a) Xie, F.; Qi, Z.; Yu, S.; Li, X. J Am Chem Soc 2014, 136,
4780-4787. (b) Ackermann, L.; Lygin, A. V. Org. Lett. 2011, 13,
3332-3335. (c) Yu, D. G.; Gensch, T.; de Azambuja, F.;
Vasquez-Cespedes, S.; Glorius, F. J Am Chem Soc 2014, 136,
17722-17725. (d) Jia, J.; Shi, J.; Zhou, J.; Liu, X.; Song, Y.; Xu, H. E.;
Yi, W. Chem. Commun. 2015, 51, 2925-2928. (e) Hummel, J. R.;
Ellman, J. A. Org. Lett. 2015, 17, 2400-2403.
(12) (a) Zhang, S.; Huang, D.; Xu, G.; Cao, S.; Wang, R.; Peng, S.;
Sun, J. Org. Biomol. Chem. 2015, 13, 7920-7923. (b) Han, W.;
Zhang, G.; Li, G.; Huang, H. Org. Lett. 2014, 16, 3532-3535. (c)
Qiu, L.; Huang, D.; Xu, G.; Dai, Z.; Sun, J. Org. Lett. 2015, 17,
1810-1813.
(13) (a) Liu, B.; Li, B.; Wang, B. Chem. Commun. 2015, 51,
16334-16337. (b) Wang, H.; Tang, G.; Li, X. Angew. Chem., Int. Ed.
2015, 54, 13049-13052. (c) Wang, X.; Yu, D.-G.; Glorius, F. Angew.
Chem., Int. Ed. 2015, 54, 10280-10283. (d) Wang, N.; Li, R.; Li, L.;
Xu, S.; Song, H.; Wang, B. J. Org. Chem. 2014, 79, 5379-5385. (e)
Liu, B.; Zhou, T.; Li, B.; Xu, S.; Song, H.; Wang, B. Angew. Chem.,
Int. Ed. 2014, 53, 4191-4195. (f) Iglesias, Á.; Álvarez, R.; de Lera, Á.
R.; Muñiz, K. Angew. Chem. Int. Ed. 2012, 51, 2225-2228. (g) Chen,
X.; Goodhue, C. E.; Yu, J.-Q. J. Am. Chem. Soc. 2006, 128,
12634-12635. (h) Thu, H.-Y.; Yu, W.-Y.; Che, C.-M. J. Am. Chem.
Soc. 2006, 128, 9048-9049. (i) Hull, K. L.; Sanford, M. S. J. Am.
Chem. Soc. 2007, 129, 11904-11905. (j) Dick, A. R.; Hull, K. L.;
Sanford, M. S. J. Am. Chem. Soc. 2004, 126, 2300-2301.
(3) (a) Kulinkovich, O. G. Chem. Rev. 2003, 103, 2597-2632. (b)
Li, L.-Z.; Xiao, B.; Guo, Q.-X.; Xue, S. Tetrahedron 2006, 62,
7762-7771. (c) Wang, Y.-F.; Chiba, S. J. Am. Chem. Soc. 2009, 131,
12570-12572. (d) Kim, K.; Cha, J. K. Angew. Chem., Int. Ed. 2009,
48, 5334-5336. (e) Hurski, A. L.; Kulinkovich, O. G. Tetrahedron
Lett. 2010, 51, 3497-3500. (f) Ziegler, D. T.; Steffens, A. M.; Funk,
T. W. Tetrahedron Lett. 2010, 51, 6726-6729. (g) Rao, N. N.; Cha,
J. K. J. Am. Chem. Soc. 2015, 137, 2243-2246. (h) Mineeva, I. V.
Russ J Org Chem. 2015, 51, 341-351.
(4) (a) Jiao, J.; Nguyen, L. X.; Patterson, D. R.; Flowers, R. A.
Org. Lett. 2007, 9, 1323-1326. (b) Astashko, D. A.; Tyvorskii, V. I.
Tetrahedron Lett. 2011, 52, 4792-4794. (c) Ren, S.; Feng, C.; Loh,
T.-P. Org. Biomol. Chem. 2015, 13, 5105-5109. (d) Zhao, H.; Fan, X.;
Yu, J.; Zhu, C. J. Am. Chem. Soc. 2015, 137, 3490-3493.
(5) (a) Kleinbeck, F.; Toste, F. D. J. Am. Chem. Soc. 2009, 131,
9178-9179. (b) Trost, B. M.; Xie, J.; Maulide, N. J. Am. Chem. Soc.
2008, 130, 17258-17259. (c) Rosa, D.; Orellana, A. Org. Lett. 2011,
13, 110-113. (d) Rosa, D.; Orellana, A. Chem. Commun. 2012, 48,
1922-1924. (e) Das, P. P.; Belmore, K.; Cha, J. K. Angew. Chem.,
Int. Ed. 2012, 51, 9517-9520. (f) Parida, B. B.; Das, P. P.; Niocel, M.;
Cha, J. K. Org. Lett. 2013, 15, 1780-1783. (g) Rosa, D.; Orellana, A.
Chem. Commun. 2013, 49, 5420-5422. (h) Cheng, K.; Walsh, P. J.
Org. Lett. 2013, 15, 2298-2301. (i) Nithiy, N.; Orellana, A. Org.
Lett. 2014, 16, 5854-5857. (j) Zhang, H.; Li, C.; Xie, G.; Wang, B.;
Zhang, Y.; Wang, J. J. Org. Chem. 2014, 79, 6286-6293. (k) Li, Y.;
Ye, Z.; Bellman, T. M.; Chi, T.; Dai, M. Org. Lett. 2015, 17,
2186-2189.
(6) (a) Ritleng, V.; Sirlin, C.; Pfeffer, M. Chem. Rev. 2002, 102,
1731-1770. (b) Giri, R.; Shi, B.-F.; Engle, K. M.; Maugel, N.; Yu,
J.-Q. Chem. Soc. Rev. 2009, 38, 3242-3272. (c) Cho, S. H.; Kim, J.
Y.; Kwak, J.; Chang, S. Chem. Soc. Rev. 2011, 40, 5068-5083. (d)
Wencel-Delord, J.; Droge, T.; Liu, F.; Glorius, F. Chem. Soc. Rev.
2011, 40, 4740-4761. (e) Ackermann, L. Chem. Rev. 2011, 111,
1315-1345. (f) Baudoin, O. Chem. Soc. Rev. 2011, 40, 4902-4911. (g)
Sun, C.-L.; Li, B.-J.; Shi, Z.-J. Chem. Rev. 2011, 111, 1293-1314. (h)
Kuhl, N.; Hopkinson, M. N.; Wencel-Delord, J.; Glorius, F.
Angew. Chem. Int. Ed. 2012, 51, 10236-10254. (i) Zhang, M.; Zhang,
Y.; Jie, X.; Zhao, H.; Li, G.; Su, W. Org. Chem. Front. 2014, 1,
843-895.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(7) (a) Colby, D. A.; Bergman, R. G.; Ellman, J. A. Chem. Rev.
2010, 110, 624-655. (b) Colby, D. A.; Tsai, A. S.; Bergman, R. G.;
Ellman, J. A. Acc. Chem. Res. 2012, 45, 814-825. (c) Song, G.;
Wang, F.; Li, X. Chem. Soc. Rev. 2012, 41, 3651-3678. (d) Kuhl, N.;
Schröder, N.; Glorius, F. Adv. Synth. Catal. 2014, 356, 1443-1460.
(e) Song, G.; Li, X. Acc. Chem. Res. 2015, 48, 1007-1020. (f) Ye, B.;
Cramer, N. Acc. Chem. Res. 2015, 48, 1308-1318.
(14) Control experiments confirmed that the D incorporation
did not originated from post-coupling H/D exchange.
(15) Park, S.-B.; Cha, J. K. Org. Lett. 2000, 2, 147-149.
ACS Paragon Plus Environment