Manganese-catalyzed allylation: Via sequential C-H and C-C/C-Het bond activation

Article abstract of DOI:10.1039/c7sc00230k

Manganese-catalyzed sequential C-H and C-C/C-Het bond activation to synthesize allylic alcohols, allylated arenes, functionalized cyclopentenes and skipped dienes is reported. This protocol can be readily scaled up and various coupling partners are applied in manganese catalysis for the first time. Moreover, manganese-catalyzed alkenyl C(sp²)-H activation is also shown. Complimentary to the standard solution-based protocols, these reactions also proceed efficiently under neat conditions, which is unprecedented for abundant metal catalyzed C-H activation reactions.

Full text of DOI:10.1039/c7sc00230k

View Article Online
View Journal
Chemical
Science
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Q. Lu, F. J. R.
Klauck and F. Glorius, Chem. Sci., 2017, DOI: 10.1039/C7SC00230K.
This is an Accepted Manuscript, which has been through the
Volume
7 Number 1 January 2016 Pages 1–812
Royal Society of Chemistry peer review process and has been
accepted for publication.
Chemical
Science
Accepted Manuscripts are published online shortly after
www.rsc.org/chemicalscience
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 2041-6539
EDGE ARTICLE
Francesco Ricci et al.
Electronic control of DNA-based nanoswitches and nanodevices
rsc.li/chemical-science

Page 1 of 5
Chemical Science
View Article Online
DOI: 10.1039/C7SC00230K
Journal Name
RSCPublishing
COMMUNICATION
ManganeseꢀCatalyzed Allylation via Sequential C–H
and C–C/C–Het Bond Activation
Cite this: DOI: 10.1039/x0xx00000x
Qingquan Lu,a Felix J. R. Klaucka and Frank Glorius*a
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/
Manganeseꢀcatalyzed sequential C−H and C−C/C−Het bond different functional groups into one molecule in a single step.9
activation to synthesize allylic alcohols, allylated arenes, However, most of the examples reported to date suffer from the
functionalized cyclopentenes and skipped dienes is reported. requirement for precious transition metal catalysts and
This protocol can be readily scaled up and various coupling stoichiometric activators. Very recently, a manganeseꢀcatalyzed
partners are applied in manganese catalysis for the first time. substitutive C–H allylation through highly selective C–H/C–O
Moreover, manganeseꢀcatalyzed alkeny C(sp2)–H activation functionalizations was achieved by Ackermann et al.8k Owing to our
is also shown. Complimentary to the standard solutionꢀbased continuous interest in 3dꢀtransition metal catalysis, we questioned
protocols, these reactions also proceed efficiently under neat whether manganese catalysis can serve as an alternative route to
condition, which is unprecedented for abundant metal integrate C–H activation with thermodynamically nonꢀfavoured βꢀ
catalyzed C–H activation reactions.
carbon/ꢀhetero atom elimination, which is largely unexplored in this
field.
Complimentary to the noble fifthꢀ and sixthꢀrow metals, direct
C–H activation1 using 3dꢀtransition metal catalysis has
fascinated chemists owing to their abundance, low price and
low toxicity, as well as to their potential to promote novel
reactivity.2 Over the past years, the goal of achieving
sustainability in organic synthesis has propelled important
research in this field and significant progress has been made.
Baseꢀmetals with flexible redox ability, such as Fe,3 Co,4 Ni,5
Cu6 have been extensively used in organometallic C–H
activation today. In contrast to being the third most abundant
transition metal, manganese is comparatively underutilized.7
Manganeseꢀmediated stoichiometric C–H activation has been
explored since 1970s, however, catalytic variants of these reactions
have proved challenging.7 Recently, the groups of Kuninobu and
Takai, Wang, Ackermann and others have significantly advanced
this field of research.8 Manganese catalysts have been found to be
versatile as they can display unique reactivity and enable C−H
functionalizations with a variety of coupling partners containing
polar multiple bonds.8 Mechanistically, these reactions mainly
involve the formal addition of a metallacycle to an unsaturated
Scheme 1. Mnꢀcatalyzed sequential C–H and C–C/C–Het activation.
To date, cyclometalation has been the most straightforward and
common method for the activation of C–H bonds. Such processes
rely mainly on solventꢀbased techniques. From a sustainability
perspective, solventꢀfree C–H activation processes are highly
desirable. Recently, rhodium(III) and iridium(III) catalyzed C–H
functionalizations under solventꢀfree conditions using a ball mill
have been reported by Bolm and coꢀworkers.10 However, to the best
of our knowledge, firstꢀrow transition metal catalyzed C–H
activation under neat condition has not been developed thus far.
Herein, our manganese catalyzed coupling offers an environmentally
friendly, operationally simple alternative to the more traditional
solventꢀbased protocols, featuring a cheap catalytic system. In this
report, various coupling partners, including vinylꢀ1,3ꢀdioxolanꢀ2ꢀone,
2ꢀvinyloxirane, vinylcyclopropane and diazabicycle are applied in
manganese catalysis for the first time, leading to the convenient
reaction partner or
a
substitution reaction.8 In recent years,
considerable efforts have been made to develop processes that can
merge C−H activation with challenging C−C/C–Het cleavage
reactions, which could allow for the efficient introduction of two
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 1

Chemical Science
Page 2 of 5
COMMUNICATION
VJieowuArrtnicalelONnlainme e
DOI: 10.1039/C7SC00230K
synthesis of allylic alcohols, allylated arenes, functionalized
cyclopentenes and skipped dienes (Scheme 1).
substrates but also amenable to benzeneꢀ and thiopheneꢀ
containing substrates, furnishing the corresponding products 3i
ꢀ
We started our investigation by reacting
Nꢀ(2ꢀpyridyl)ꢀindole
3k in good yields. Furthermore, an ꢀpyrimidyl moiety could
N
(
1a) with vinylꢀ1,3ꢀdioxolanꢀ2ꢀone (2aa) under Mn2(CO)10
be employed as a directing group and the expected product 3l
was isolated in 79% yield. Notably, this reaction also exhibited
high efficiency on a large scale. The desired product 3a could
be isolated in 91% yield (1.44 g) on a 6ꢀmmol scale. In
addition, this protocol was also successfully applicable to 2ꢀ
vinyloxiranes, as the coupling partner, and the products 3a and
3g were isolated in 54% and 69% yield respectively.
Encouraged by these inspiring results, we then pursued more
challenging successive C–H/C–C activation. Gratifyingly, fine
tuning of the reaction conditions allowed the coupling of 1a
with dimethyl 2ꢀvinylcyclopropaneꢀ1,1ꢀdicarboxylate (2ba) to
proceed smoothly under solvent free or concentrated DMF
conditions (Scheme 3). Both electronꢀrich (ꢀOMe) and electron
o
catalysis in diethyl ether at 80 C. This transformation involves
the cleavage of a stable C−O bond to form an easily modifiable
C=C bond and an alcohol moiety. To our delight, the desired
product 3a could be isolated in 41% yield (for details, see table
S1 in ESI). Subsequently, employing [MnBr(CO)5] as the
catalyst precursor afforded product 3a in 84% yield in the
presence of sodium acetate. The yield of 3a could be further
improved to 90% by increasing the temperature to 90 oC.
Notably, the reaction occurred most efficiently in the absence
of solvent and 92% yield of 3a could be isolated. Further
experiments showed that Mn(OAc)2•4H2O or Cp*Mn(CO)3 in
lieu of [MnBr(CO)5] are ineffective. Additionally, manganese
is essential for this transformation as in its absence no reaction
occurred.
deficient (ꢀF, ꢀBr, ꢀI)
Nꢀ(2ꢀpyridyl)ꢀindoles are amenable to this
method, giving the corresponding products 4b
ꢀ
4e in 52ꢀ90%
yields. A 3ꢀmethyl substituent did not diminish the reactivity,
as demonstrated by the formation of the desired products 4f and
4g in excellent yields. Moreover, the scope of the arene
substrate could further be extended to phenylpyridine and
[MnBr(CO)5] (10 mol%)
NaOAc (20 mol%)
DG
DG
O
O
Ar
Ar
90 oC, Et2O or neat
O
OH
1
2aa
3
CN
thiophene derivatives, affording the corresponding products 4h
ꢀ
4j in moderate yields.
N
2-py
N
2-py
F
N
2-py
OH
OH
OH
DG
DG
[Mn2(CO)10] (10 mol%)
90 oC, DMF or neat
E
a
3c 91% (6.8:1)
3a
90% (7.0:1), 92% (4.0:1)
91% (6.7:1)b, 54% (2.8:1)c,d
d
Ar
3b
75% (4.4:1)
Ar
E
E
R1
E = CO2Me
E
X
1
2ba
4
N
R2
N
2-py
N
2-py
E
E
E
E
E
OH
OH
89% (5.3:1)
R1 = Me, R2 = H; 3f 97% (5.4:1)
R1 = Me, R2 = Me; 3g 69% (1:1.2)d,e
R1 = CHO, R2 = H; 3h 93% (3.1:1)
Br
E
OH
OH
3d
X = Br,
3i
71% (6.9:1)
X = I, 3e 91% (5.7:1)
N
2-py
4a 75% (2.6:1)a
N
2-py
N
2-py
F
4b 87% (2.3:1)
4c 63% (2.5:1)
N
N
E
E
E
E
N
S
N
I
O
E
E
N
MeO
OH
N
2-py
N
2-py
N
2-py
OH
3j 81% (5.2:1)a
3k 70% (4.7:1)a
3l 79% (4.8:1)
4f 89% (1.8:1)a
E = CO2Et; 4g 95% (2.1:1)a
4d 52% (2.3:1)
4e 90% (2.7:1)
Scheme 2. Unless otherwise specified, all reactions were carried out using 1
(0.2 mmol), 2 (0.3 mmol), [MnBr(CO)5] (10 mol%), and NaOAc (20 mol%)
in Et2O (1.0 mL) at 90 oC under argon for 5 h, isolated yield, E/Z value given
E
E
N
E
N
E
N
a
b
E
in parentheses. neat. reaction performed on a 6 mmol scale with 47 h
E
c
e
reaction time. 2ꢀvinyloxirane (0.6 mmol) was used instead of 2aa. d 10 h.
O
S
2ꢀmethylꢀ2ꢀvinyloxirane (0.6 mmol) was used instead of 2aa.
4h 57% (2.6:1)a
4i 50%(4.7:1)b,c
4j 53% (3.0:1)
Scheme 3. Unless otherwise specified, all reactions were carried out using 1
(0.2 mmol), 2 (0.3 mmol), and Mn2(CO)10 (10 mol%) in DMF (0.2 mL) at 90
With the optimized reaction conditions in hand, the
generality of this protocol was first tested by reaction of indole
heterocycles with 2aa and the results are given in Scheme 2.
Compared to the neat condition, our studies showed that the
a
oC under argon for 24 h, isolated yield, E/Z value given in parentheses.
[MnBr(CO)5] (10 mol%) and NaOAc (20 mol%) were used under neat
condition. b neat. c Mn2(CO)10 (20 mol%).
product 3a could be isolated in higher
ether was used. Indoles substituted with reactive electrophilic
functional groups which can undergo subsequent
functionalization, such as the halides (ꢀF, ꢀBr, ꢀI) and cyano
substituents, were well tolerated. Introduction of a methyl or
formyl group at the 3ꢀposition of the indole ring had no
E/Z ratios when diethyl
Considering the importance of nitrogenꢀcontaining
compounds and the ease of further transformation on this
moiety, we next sought to apply our developed protocol to
introduce a vicinal 2ꢀarylated cyclopentenylamine unit. These
are known to be key structures found within biologically active
small molecules and are key intermediates in the synthesis of
pharmaceutically important cyclopentane derivatives.[9e]
Pleasingly, when diazabicycle 2ca was utilized, the desired
influence on the reaction efficiency (3f
reaction tolerates steric bulk in the proximity of the reaction
center of . Moreover, this protocol was not restricted to indole
ꢀ3h), indicating that the
1
arylꢀ, amineꢀsubstituted cyclopentenes 5aꢀ5g were obtained in
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 3 of 5
Journal Name
Chemical Science
View Article Online
COMMUNICATION
DOI: 10.1039/C7SC00230K
70%–94% yields (Scheme 4). Not only
Nꢀ(2ꢀpyridyl)ꢀindoles, Approximately 71% deuterium was incorporated into recovered
but also phenylpyridines were suitable substrates. It is 1a when sodium acetate was replaced with [MnBr(CO)5].
important to note that this reaction also proved to be efficient Furthermore, a larger deuterium incorporation (85%) at the 2ꢀ
under neat condition. Arguably, this is the first example of a position of 1a was observed when 1a was treated with CD3OD
firstꢀrow transition metal catalyzed C–H activation/sixꢀ in the presence of both [MnBr(CO)5] and sodium acetate. These
membered ring scission sequence.
results suggest that the C–H activation step is reversible and
might occur via a baseꢀassisted cyclometalation process. In
addition, a kH/kD = 1.0 was observed from parallel reactions of
1a and [D]ꢀ1a with 2aa respectively, which suggests that the
cleavage of the C−H bond is not involved in the rateꢀ
determining step. Furthermore, when (3ꢀpyridyl)ꢀthiophene was
utilized, the reaction occurred exclusively at the more electron
rich 2ꢀposition (Scheme 6). On the basis of aboveꢀmentioned
results, we may draw the conclusion that olefin coordination
and insertion step is the rateꢀdetermining step, and that the
elimination is a facile process.11
βꢀ
Scheme 6. Intramolecular C–H competition experiment.
Table 1. Exploration of the influencing factor for the reaction selectivity.a
Scheme 4. Unless otherwise specified, all reactions were carried out using 1
(0.2 mmol), 2 (0.3 mmol), [MnBr(CO)5] (10 mol%) and NaOAc (20 mol%)
a
b
in Et2O (1.0 mL) at 90 oC under argon for 10 h, isolated yield. 37 h.
[MnBr(CO)5] (20 mol%) and NaOAc (40 mol%) were used under neat
condition at 100 oC for 37 h.
Entry
1
Temp. / ºC
90
Time / h
5
Solvent
Et2O
Yield
89
Ratio E/Z
Olefinic C−H activation could also be achieved under these
7.0
conditions. For example, 2ꢀ(propꢀ1ꢀenꢀ2ꢀyl)pyridine
(1m)
2
3
4
5
90
60
90
90
10
10
10
5
Et2O
Et2O
DMF
ꢀ
89
57
55
92
6.9
6.8
performed well in this transformation and the desired products
3m and 5g, a skipped diene with a valuable handle for further
derivatization, were obtained in 75% and 62% yield
respectively (Scheme 5).
3.4
4.0
a
All reactions were carried out using 1a (0.2 mmol), 2aa (0.3 mmol),
[MnBr(CO)5] (10 mol%) and NaOAc (20 mol%) under different conditions,
isolated yield, E/Z ratio is determined by 1H NMR.
To acquire a better understanding of the observed reaction
selectivity, a series of experiments were performed. As shown
in Table 1, no obvious isomerization of the C=C bond was
observed regardless of prolonged reaction time or decreased
reaction temperature (Entries 1ꢀ3, Table 1). On the contrary,
Scheme 5. Manganeseꢀcatalyzed alkenyl C−H activation.
This transformation is presumed to proceed through an
organometallic C–H activation process, as was supported by
radical trapping experiments (for details, see Scheme S1 in the
ESI). The reaction of 1a and 2aa under standard condition was
solvent was found to have a dramatic effect on the
selectivity (Entries 3ꢀ5, Table 1). Compared to the neat
reaction, DMF had a negative effect to the final selectivity,
while diethyl ether had a positive effect. From these results, we
inferred that the involvement of the πꢀallylmanganese
intermediate in the reaction mechanism might be excluded and
that the solvent imparts selectivity during this transformation.
E/Z
E/Z
found to be compatible with radical scavenges, 2,4ꢀdiꢀtert
ꢀ
butylꢀ4ꢀmethylphenol (BHT) and 1,1ꢀdiphenylethylene.
To gain more insight into the reaction mechanism, H/D
scrambling experiments were next conducted (for details, see
ESI). No H/D exchange at the 2ꢀposition of 1a was observed
when 1a was simply mixed with CD3OD and sodium acetate.
Conclusions
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 3

Chemical Science
Page 4 of 5
COMMUNICATION
VJieowuArrtnicalelONnlainme e
DOI: 10.1039/C7SC00230K
In conclusion, we have developed a general strategy to
synthesize allylic alcohols, allylated arenes, functionalized
cyclopentenes and skipped dienes, in which earth abundant
manganese was utilized as the catalyst. This protocol represents
a combination of C−H and C−C/C−Het bond activation. Both
aromatic and olefinic substrates are functionalized in this
reaction. This work broadens the scope of manganese catalysis
to include a series of new coupling partners. Additionally, this
reaction can occur efficiently under neat condition yet does not
require the use of a large excess of a coupling partner as
solvent, which is unprecedented in abundant metal catalysis.
2015, 48, 1194; (e) M. Moselage, J. Li and L. Ackermann, ACS
Catal., 2015, 498; (f) N. Yoshikai, ChemCatChem, 2015,
C. L. C. Misal and C. Naoto, Chem. Lett., 2015, 44, 410.
7, 732.
5
6
(a) O. Daugulis, H.ꢀQ. Do and D. Shabashov, Acc. Chem. Res., 2009,
42, 1074; (b) A. E. Wendlandt, A. M. Suess and S. S. Stahl, Angew.
Chem. Int. Ed., 2011, 50, 11062; (c) S. Gaillard, C. S. J. Cazin and S.
P. Nolan, Acc. Chem. Res., 2012, 45, 778; (d) X.ꢀX. Guo, D.ꢀW. Gu,
Z. Wu and W. Zhang, Chem. Rev., 2015, 115, 1622; (e) J. Liu, G.
Chen and Z. Tan, Adv. Synth. Catal., 2016, 358, 1174.
7
8
(a) C. Wang, Synlett, 2013, 24, 1606; (b) W. Liu and L. Ackermann,
ACS Catal., 2016, 6, 3743.
Finally, βꢀcarbon and βꢀnitrogen elimination were shown to be
(a) Y. Kuninobu, Y. Nishina, T. Takeuchi and K. Takai, Angew.
Chem. Int. Ed., 2007, 46, 6518; (b) B. Zhou, H. Chen and C. Wang,
J. Am. Chem. Soc., 2013, 135, 1264; (c) R. He, Z. T. Huang, Q. Y.
Zheng and C. Wang, Angew. Chem. Int. Ed., 2014, 53, 4950; (d) B.
feasible under lowꢀvalent manganese catalysis for the first time.
This work was supported by the Alexander von Humboldt
Foundation (Dr. Q. Lu) and the Fonds der Chemischen
Industrie (F.J.R.K.). We also thank Dr. Kathryn M. Chepiga
and Suhelen VásquezꢀCéspedes for helpful discussions.
Zhou, P. Ma, H. Chen and C. Wang, Chem. Commun., 2014, 50
,
14558; (e) W. Liu, J. Bang, Y. Zhang and L. Ackermann, Angew.
Chem. Int. Ed., 2015, 54, 14137; (f) W. Liu, D. Zell, M. John and L.
Ackermann, Angew. Chem. Int. Ed., 2015, 54, 4092; (g) L. Shi, X.
Zhong, H. She, Z. Lei and F. Li, Chem. Commun., 2015, 51, 7136;
Notes and references
a
OrganischꢀChemisches Institut, Westfälische WilhelmsꢀUniversität
(h) B. Zhou, Y. Hu and C. Wang, Angew. Chem. Int. Ed., 2015, 54
,
Münster, Corrensstraße 40, 48149 Münster (Germany). Eꢀmail:
glorius@uniꢀmuenster.de.
13659; (i) Y.ꢀF. Liang, L. Massignan, W. Liu and L. Ackermann,
Chem. Eur. J., 2016, 22, 14856; (j) W. Liu, S. C. Richter, R. Mei, M.
Feldt and L. Ackermann, Chem. Eur. J., 2016, 22, 17958; (k) W. Liu,
† Electronic Supplementary Information (ESI) available: See DOI:
10.1039/c000000x/.
S. C. Richter, Y. Zhang and L. Ackermann, Angew. Chem. Int. Ed.
,
,
1
Selected reviews, see: (a) D. A. Colby, R. G. Bergman and J. A.
Ellman, Chem. Rev., 2010, 110, 624; (b) T. W. Lyons and M. S.
Sanford, Chem. Rev., 2010, 110, 1147; (c) L. Ackermann, Chem.
Rev., 2011, 111, 1315; (d) S. H. Cho, J. Y. Kim, J. Kwak and S.
Chang, Chem. Soc. Rev., 2011, 40, 5068; (e) L. McMurray, F. O'Hara
and M. J. Gaunt, Chem. Soc. Rev., 2011, 40, 1885; (f) T. Newhouse
and P. S. Baran, Angew. Chem. Int. Ed., 2011, 50, 3362; (g) J.
2016, 55, 7747; (l) S. Sueki, Z. Wang and Y. Kuninobu, Org. Lett.
2016, 18, 304; (m) N. P. Yahaya, K. M. Appleby, M. Teh, C.
Wagner, E. Troschke, J. T. W. Bray, S. B. Duckett, L. A.
Hammarback, J. S. Ward, J. Milani, N. E. Pridmore, A. C.
Whitwood, J. M. Lynam and I. J. S. Fairlamb, Angew. Chem. Int. Ed.
,
2016, 128, 12643; (n) X. Yang, X. Jin and C. Wang, Adv. Synth.
Catal., 2016, 358, 2436; (o) Y. Hu and C. Wang, Sci. China Chem.
,
,
WencelꢀDelord, T. Droge, F. Liu and F. Glorius, Chem. Soc. Rev.
,
2016, 59, 1301.
2011, 40, 4740; (h) C. S. Yeung and V. M. Dong, Chem. Rev., 2011,
111, 1215; (i) K. M. Engle, T.ꢀS. Mei, M. Wasa and J.ꢀQ. Yu, Acc.
Chem. Res., 2012, 45, 788; (j) N. Kuhl, M. N. Hopkinson, J. Wencelꢀ
Delord and F. Glorius, Angew. Chem. Int. Ed., 2012, 51, 10236; (k) J.
9
For examples, see: (a) C. Aïssa and A. Fürstner, J. Am. Chem. Soc.
2007, 129, 14836; (b) E. Jijy, P. Prakash, M. Shimi, P. M. Pihko, N.
Joseph and K. V. Radhakrishnan, Chem. Commun., 2013, 49, 7349;
(c) S. Yu and X. Li, Org. Lett., 2014, 16, 1200; (d) S.ꢀS. Zhang, J.ꢀQ.
Wu, Y.ꢀX. Lao, X.ꢀG. Liu, Y. Liu, W.ꢀX. Lv, D.ꢀH. Tan, Y.ꢀF. Zeng
and H. Wang, Org. Lett., 2014, 16, 6412; (e) Y. Zhang, Q. Wu and S.
Yamaguchi, A. D. Yamaguchi and K. Itami, Angew. Chem. Int. Ed.
,
,
,
,
,
,
,
2012, 51, 8960; (l) C. Zhu, R. Wang and J. R. Falck, Chem. Asian J.
2012,
2013,
7
, 1502; (m) J. WencelꢀDelord and F. Glorius, Nat Chem
Cui, Chem. Sci., 2014, 5, 297; (f) J.ꢀQ. Wu, Z.ꢀP. Qiu, S.ꢀS. Zhang,
5, 369; (n) C. Zheng and S.ꢀL. You, RSC Advances, 2014,
4
J.ꢀG. Liu, Y.ꢀX. Lao, L.ꢀQ. Gu, Z.ꢀS. Huang, J. Li and H. Wang,
6173; (o) O. Daugulis, J. Roane and L. D. Tran, Acc. Chem. Res.
2015, 48, 1053; (p) G. Qiu and J. Wu, Org. Chem. Front., 2015,
169; (q) P. Gandeepan and C.ꢀH. Cheng, Chem. Asian J., 2016, 11
Chem. Commun., 2015, 51, 77; (g) S.ꢀS. Zhang, J.ꢀQ. Wu, X. Liu and
2
H. Wang, ACS Catal., 2015, 5, 210; (h) L. Kong, S. Yu, G. Tang, H.
Wang, X. Zhou and X. Li, Org. Lett., 2016, 18, 3802; (i) S. Sharma,
S. H. Han, Y. Oh, N. K. Mishra, S. Han, J. H. Kwak, S.ꢀY. Lee, Y. H.
Jung and I. S. Kim, J. Org. Chem., 2016, 81, 2243; (j) D. Zell, Q. Bu,
M. Feldt and L. Ackermann, Angew. Chem. Int. Ed., 2016, 55, 7408.
448; (r) T. Gensch, M. N. Hopkinson, F. Glorius and J. Wencelꢀ
Delord, Chem. Soc. Rev., 2016, 45, 2900.
2
3
(a) A. A. Kulkarni and O. Daugulis, Synthesis, 2009, 4087; (b) M. C.
White, Adv. Synth. Catal., 2016, 358, 2364.
10 (a) G. N. Hermann, P. Becker and C. Bolm, Angew. Chem. Int. Ed.
,
,
(a) C. Bolm, J. Legros, J. Le Paih and L. Zani, Chem. Rev., 2004,
104, 6217; (b) E. Nakamura and N. Yoshikai, J. Org. Chem., 2010,
2015, 54, 7414; (b) J. G. Hernandez and C. Bolm, Chem. Commun.
2015, 51, 12582; (c) G. N. Hermann, P. Becker and C. Bolm, Angew.
Chem. Int. Ed., 2016, 55, 3781.
75, 6061; (c) C. L. Sun, B. J. Li and Z. J. Shi, Chem. Rev., 2011, 111
,
1293; (d) I. Bauer and H.ꢀJ. Knölker, Chem. Rev., 2015, 115, 3170.
11 A mechanism was proposed in Scheme S3 in the ESI.
12 Only trace amount of the desired products can be detected when 4ꢀ
(hexꢀ1ꢀenꢀ2ꢀyl)ꢀ1,3ꢀdioxolanꢀ2ꢀone or dimethyl 2ꢀ(propꢀ1ꢀenꢀ2ꢀ
yl)cyclopropaneꢀ1,1ꢀdicarboxylate was utilized under the optimized
conditions.
4
(a) N. Yoshikai, Synlett, 2011, 1047; (b) L. Ackermann, J. Org.
Chem., 2014, 79, 8948; (c) K. Gao and N. Yoshikai, Acc. Chem. Res.
2014, 47, 1208; (d) P. Gandeepan and C.ꢀH. Cheng, Acc. Chem. Res.
,
,
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 5 of 5
Journal Name
Chemical Science
View Article Online
COMMUNICATION
DOI: 10.1039/C7SC00230K
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 5