MnI/AgI Relay Catalysis: Traceless Diazo-Assisted C(sp2)–H/C(sp3)–H Coupling to β-(Hetero)Aryl/Alkenyl Ketones

Article abstract of DOI:10.1002/anie.201803384

An unprecedented Mn^I/Ag^I-relay-catalyzed C(sp²)?H/C(sp³)?H coupling of (vinyl)arenes with α-diazoketones is reported, wherein the diazo group was exploited as a traceless auxiliary for control of regioselectivity. Challenging β-(hetero)aryl/alkenyl ketones were obtained through this operationally simple approach. The cascade process merges denitrogenation, carbene rearrangement, C?H activation, and hydroarylation/hydroalkenylation. The robustness of this method was demonstrated at preparative scale and applied to late-stage diversification of natural products.

Full text of DOI:10.1002/anie.201803384

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Accepted Article
Title: Mn(I)/Ag(I) Relay Catalysis: Traceless Diazo-Assisted C(sp2)-H/
C(sp3)-H Coupling to beta-(Hetero)Aryl/Alkenyl Ketones
Authors: Qingquan Lu, Shobhan Mondal, Sara Cembellín, and Frank
Glorius
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201803384
Angew. Chem. 10.1002/ange.201803384
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2
Mn(I)/Ag(I) Relay Catalysis: Traceless Diazo-Assisted C(sp )–
3
H/C(sp )–H Coupling to -(Hetero)Aryl/Alkenyl Ketones
Qingquan Lu, Shobhan Mondal, Sara Cembellín and Frank Glorius*
Dedicated to Prof. Xiyan Lu on the occasion of his 90th birthday
2
enones.[8] However, enones (especially of alkyl enones), which
are often derived from their saturated analogues using
Abstract: An unprecedented Mn(I)/Ag(I) relay-catalyzed C(sp )–
3
H/C(sp )–H coupling of (vinyl)arenes with -diazoketones is reported,
[
9]
wherein the diazo group was exploited as a traceless auxiliary for
control of regioselectivity. Challenging -(hetero)aryl/alkenyl ketones
were obtained via this operationally simple approach. The cascade
process merges denitrogenation, carbene rearrangement, C–H
activation and hydroarylation/hydroalkenylation. The robustness of
this methodology was exhibited at preparative scale and applied to
late-stage diversification of natural products.
stoichiometric oxidants, are limited to terminal/activated enones
or 2-cyclohexenone/2-cyclopentenone derivatives in most of
reported methods.[ Transition-metal-catalyzed tandem ketone
dehydrogenation and conjugate addition has emerged as an
8]
alternative.[
7,
10]
While -arylation of cyclohexanone derivatives
with aryl halides or aryl-metal reagents is known, derivatization of
linear ketones and macrocyclic ketones remains challenging.
Furthermore, necessity of air-sensitive ligands and stoichiometric
oxidants decreases practicality of these reactions.[
7, 10]
Therefore,
C–H bond activation has become one of the most powerful
methods to access valuable molecules from readily available
hydrocarbons.[1] In this regard, the pursuit of more sustainable,
efficient catalyst systems has been of long-standing interest.
Distinct catalyst systems employing manganese, an abundant,
economical and low toxicity transition metal, have received great
attention and been developed by the groups of Kuninobu and
Takai,[ Wang, Ackermann, Glorius and others. Despite
these major advances, discovery of novel manganese systems
and site-selective C–H/C–H crossing coupling reactions remain
an extremely attractive yet challenging goal.
it is highly desirable to find new strategies to access these
compounds.
Diazo compounds can be easily prepared from the
corresponding ketones and are widely used in organic
synthesis.[12] In principle, they are known to react with
[11]
organometallic species to generate metal carbene intermediates,
which in turn undergo rapid migratory insertion to furnish alkylated
2]
[3]
[4]
[5]
[6]
[13]
products (Scheme 1a, LG: leaving group).
This general
protocol has been extensively explored using Ir, Pd, Rh, Ru, Co,
[13]
Cu etc, whereas Mn has been seldom studied in this area.
Additionally, the Wang group has developed a pioneering amine-
accelerated Mn-catalyzed aromatic C–H conjugate addition to

,-unsaturated carbonyls (Scheme 1b).[3c] Compared with
acrylates, enones showed much lower reactivity in this protocol.
Furthermore, presumably owing to predominately undesired β-H
elimination of alkyl-M species formed by migratory insertion of
3
carbene into C-M bond, activation of a C(sp )–H bond of diazo
compounds remains largely undeveloped. On this basis, we
reasoned that the remarkable difficulty of β-H elimination
observed in manganese catalysis might offer a new pathway to
overcome these limitations.[14] Herein, we describe a novel
2
3
Mn(I)/Ag(I) relay catalysis that enables formal C(sp )–H/C(sp )–
H
coupling to generate -(hetero)aryl/alkenyl ketones with
exclusive regioselectivity, in which -diazoketones were used as
ketone equivalents (Scheme 1c). This operationally simple
approach is highly effective with previously challenging linear and
macrocyclic ketones, including unbiased dialkyl ketones,
exhibiting switchable selectivity.
To probe the feasibility of our assumption, we initially chose
N-(2-pyridyl)indole (1a) and 2-diazo-1-phenylpropan-1-one (2a)
as the standard substrates. After extensive screening of various
reaction parameters, it was found that the combination of
2
3
Scheme 1. Mn(I)/Ag(I) relay-catalyzed C(sp )–H/C(sp )–H coupling.

-(Hetero)aryl ketones are prevalent structural motifs in
pesticides, anti-oxidants, and drug candidates.[7] Typically, they
are obtained by conjugate addition of aryl-metal species to
5 4
commercially available MnBr(CO) and AgBF could offer the
2
3
[
[
*]
Dr. Q. Lu, S. Mondal, Dr. S. Cembellín and Prof. Dr. F. Glorius
Organisch-Chemisches Institut
Westfälische Wilhelms-Universität Münster
Corrensstraße 40, 48149 Münster (Germany)
E-mail: glorius@uni-muenster.de;
formal C(sp )–H/C(sp )–H coupling product 3aa in almost
quantitative yield (Scheme 2),[15] with -site selectivity of -
diazoketone being in contrast with previous reports using diazo
compound as reactant.[16]
]
This work was supported by the Alexander von Humboldt Foundation
(Q.L. and S.C.), the Deutsche Forschungsgemeinschaft (Leibniz
Award). We also thank Toryn Dalton and Hyung Yoon (both WWU)
for helpful discussions.
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The classical pathways such as the migratory insertion of
carbene into C-Mn bond and subsequent β-H elimination was
completely avoided, neither alkylated product 4aa nor alkenylated
product 4ab was detected. Moreover, 4ac, which might be formed
via the reaction of manganacycle with the Wolff rearrangement of
2
a,[17] was not observed, highlighting the high selectivity of this
reaction. Notably, this transformation can also proceed efficiently
at room temperature. Control experiments showed that no
product was observed in the absence of either MnBr(CO)
5
or
Scheme 2. All reactions were carried out using 1a (0.20 mmol), 2 (1.2 equiv.),
[
MnBr(CO)
5
] (10 mol%), AgBF
4
(20 mol%) and NaOAc (20 mol%) in DME (1.0
AgBF , demonstrating the cooperativity of these catalysts.
4
[
a]
mL) under argon for 4 h, isolated yield. 24 h.
Scheme 3. Unless otherwise specified, all reactions were performed with 1 (1.0 equiv.), 2 (1.2 equiv.), [MnBr(CO)
5
] (10 mol%), AgBF
mol%) in DME (0.2 M) at 45 C under argon for 4 h, isolated yields. RT, 24 h; 12 h, DME (0.23 M); 2 (1.5 equiv.); [d] BPh (20 mol%); [e] dioxane (0.2 M); 16
(25 mol%), NaOAc (30 mol%), BPh
(30 mol%); [n] 2 (2.5 equiv.),
(40 mol%), 24 h; [o] step 1: 2 (1.15 equiv.) and [d-g] was used, step 2: [c-g] was used.
4
(20 mol%) and NaOAc (20
o
[a]
[b]
[c]
[f]
3
[g]
o
[h]
[i]
o
[j]
o
[k]
[l]
[m]
h; 80 C; 5 h; 90 C; 100 C; 14 h; dioxane (0.1 M); [MnBr(CO)
MnBr(CO) ] (20 mol%), AgBF (40 mol%), NaOAc (40 mol%), BPh
5
] (15 mol%), AgBF
4
3
[
5
4
3
With the optimized reaction conditions in hand, the generality
compatibility with 1,2-dialkyl -diazoketones prepared from
unbiased dialkyl ketones. It addressed the challenging -
functionalization of simple ketones and provided an array of -
heteroaryl ketones (3aj-3am) in excellent yields with switchable
selectivity. Cyclic -diazoketones, especially for the medium to
macrocyclic -diazoketones, were also successfully -
heteroarylated with 1a, providing 3an and 3ao (the latter being a
Muscone analogue) in 95% and 78% yields respectively. Notably,
muscone is the main component of musk, which requires a five-
step synthesis previously for its preparation from the same ketone
in lower yield.[18] To further test the practicability of this reaction,
the late-stage manipulation of lithocholic acid and estrone
derivatives were successfully demonstrated. Heterocycles, such
of this protocol was first investigated by the reaction of 1a with-
diazo ketones. A series of alkyl-substituted, aryl -diazoketones
were viable in this transformation, providing the desired -
heteroaryl ketones (3aa-3ae) in 95% to 99% yields. The tolerance
of bromide makes this transformation orthogonal to traditional
cross-coupling.
A heteroaromatic -diazoketone, 2-diazo-1-
(
furan-2-yl)propan-1-one, was also found to be a suitable reaction
partner in this protocol (3af). Although 1,2-dialkyl -diazoketones
have multiple reaction sites, reactions occurred exclusively on the
diazo group assisted -position over reactive acidic -C–H bonds,
giving the corresponding product in excellent yield (3ag-3ao). In
addition, the generality of this protocol was demonstrated by its
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as indoles, thiophenes, benzothiophene and pyrroles, were
tolerated in this protocol and gave the -heteroaryl ketones 3ba-
alkylated product was detected, suggesting that formation of
manganese carbene might be unfavourable under this condition.
The interaction of manganese and silver with 2a was further
explored. It was found that 1-phenylprop-2-en-1-one 3a was
generated in 86% yield when 2a was directly treated with 10 mol%
3
ia in good to excellent yields. This protocol was also amenable
to 2-phenylpyridines, furnishing the corresponding -aryl ketones
ja-3ma in 87%-93% yields. Olefinic C–H activation was also
achieved by this protocol. The desired -alkenyl ketones 3na and
oa, with a valuable allyl group for further derivatization, were
3
AgBF
presence of MnBr(CO)
observed when 2a-d was used in the silver-catalyzed reaction
4
, and only a trace amount of 3a was observed in the
3
5
(Scheme 4b). Moreover, 3a-d was
3
obtained in 67% and 54% yields respectively. Interestingly,
3
double C–H activation products 3pa and 3qa can also be obtained
(for details, see the SI), clearly showing that a 1,2-hydrogen
migration process was involved.[20] Next, employing 3a under the
standard reaction conditions also afforded 3aa in 95% yield,
indicating that 3a might be an intermediate (Scheme 4c). We next
attempted to use gas chromatography to monitor the reaction
between 1a and 2a. The kinetic profiles (Scheme 4d) clearly
showed that 2a was fully consumed within 30 min, and 3a was
formed simultaneously. Afterwards, the desired product 3aa
increased gradually in intensity with the consumption of 3a. These
results demonstrated that this transformation proceeds via a
tandem denitrogenation-carbene rearrangement-hydroarylation/
C–H activation sequence. Additionally, intermolecular competition
experiments showed that electron-rich indole and electron-
deficient -diazoketone were more reactive in this transformation.
2
in 94% and 49% yields. Furthermore, a stepwise C(sp )–
3
H/C(sp )–H coupling of 2-(thiophen-3-yl)pyridine with two -
diazoketones provided the desired product 3ra in 54% yield. More
generally, this approach could be extended to -heteroarylation of
an -diazoketone, for example, 3sa could be obtained in
moderate yield.[19] It is noteworthy that this protocol can be readily
scaled up to gram quantities with high efficiency. For instance,
1.13 g of the -heteroaryl ketone 3aa was isolated in 99% yield
without sacrificing the yield. Notably, the loading of manganese
catalyst and silver salt can be decreased to 2.5 mol% and 5 mol%,
respectively, furnishing the desired product 3aa in 90% yield (for
details, see the SI).
9
1
2
3
3
a
a
a
aa
6
3
0
Scheme 5. Proposed mechanism.
0
2
4
6
8
10
Time / h
Based on the aforementioned results and previous studies,[14,
a mechanism was proposed in Scheme 5. A silver-catalyzed,
20]
Scheme 4. Mechanistic studies.
denitrogenation-carbene rearrangement of 2a generates 3a.
Meanwhile, base-assisted cyclomanganation of 1a gives an
organomanganese specie, which is followed by enone insertion
and subsequent protonation to liberate desired -aryl ketone. The
fast 1,2-hydrogen migration, but slower carbene migratory
insertion, β-H elimination and unfavourable Wolff rearrangement
ensures high reaction selectivity, enabling the facile synthesis of
structurally diverse -aryl/alkenyl ketones.
To gain insight into the reaction mechanism, a series of
experiments were conducted (for details, see the SI). First, H/D
scrambling experiments revealed that C–H activation step is
reversible and might occur via a base-assisted cyclometalation
process. Moreover, AgBF
presence did not affect the Mn-catalyzed C–H activation step.
Furthermore, a minor kinetic isotope effect (k /k = 1.29) was
4
did not activate the C–H bond and its
In summary, we have developed a new approach to the
synthesis of -(hetero)aryl/alkenyl ketones via Mn(I)/Ag(I) relay
catalysis, many of which are difficult to access using previously
reported methods. This unique strategy opens up a new channel
H
D
observed from parallel reactions of 1a and [D]-1a with 2a,
indicating that cleavage of C–H bond is unlikely to be involved in
the rate-determining step. In addition, an isotope labeling
experiment elucidated that the hydrogen atom in the product 3aa
originates from -diazoketone 2a (Scheme 4a). Subsequently,
methyl diazoacetoacetate and aryl diazoester, which have been
reported to form metal carbene intermediates in transition metal-
catalyzed C–H activation,[16c, 16d] were used to determine whether
a manganese carbene was involved in this reaction. However, no
3
to couple metal-catalyzed C–H activation with -C(sp )–H
functionalization of -diazoketone, which can be performed on a
broad substrate scope derived from diverse ketones.
Keywords: manganese • C−H activation • relay catalysis • -
heteroaryl ketone • -diazoketone
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Angewandte Chemie International Edition
10.1002/anie.201803384
COMMUNICATION
COMMUNICATION
Qingquan Lu, Shobhan Mondal, Sara
Cembellín and Frank Glorius*
Page No. – Page No.
Mn(I)/Ag(I) Relay Catalysis: Traceless
2
3
Diazo-Assisted C(sp )–H/C(sp )–H
Coupling to -(Hetero)Aryl/Alkenyl
Ketones
2
3
Forward Together! An unprecedented Mn(I)/Ag(I) relay-catalyzed C(sp )–H/C(sp )–H
coupling of (vinyl)arenes with -diazoketones is reported, wherein diazo group was
exploited as traceless auxiliary for control of regioselectivity. This unique strategy opens
3
up a new channel to couple transition metal-catalyzed C–H activation with -C(sp )–H
functionalization of -diazoketone, which efficiently merges denitrogenation, carbene
rearrangement, C–H activation and hydroarylation/hydroalkenylation.
This article is protected by copyright. All rights reserved.