Gold-catalyzed: Para -selective C-H bond alkylation of benzene derivatives with donor/acceptor-substituted diazo compounds

Article abstract of DOI:10.1039/c7cc05649d

Herein, we report a gold-catalyzed highly site-selective C(sp²)-H functionalization of unactivated arenes with α-aryl-α-diazoesters with electron-withdrawing substituents as induced groups on aryl rings. Furthermore, the induced groups are useful for further synthetic transformations.

Full text of DOI:10.1039/c7cc05649d

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
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3
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Gold-catalyzed para-selective C-H bond alkylation of benzene
derivatives with donor/acceptor-substituted diazo compounds
Received 00th January 20xx,
Accepted 00th January 20xx
Ben Ma, Jiaojiao Wu, Lu Liu* and Junliang Zhang*
DOI: 10.1039/x0xx00000x
www.rsc.org/
2
2
Herein, we reported a gold-catalyzed highly site-selective C(sp )–H wish to present here our results on para-selective C(sp )-H bond
functionaliztion of unactivated arenes and α-aryl-α-diazoesters functionalization of unactivated arenes (Scheme 1c).
with electron-withdrawing substituents as induced groups on aryl
a) Previous work:
CO
2
R2
R'
R
rings. Furthermore, the induced groups are useful for further
synthetic transformations.
R
R1
R
N
2
Metal
R2
2
CO
R1
+
or
or
R1
R2
CO
2
R1
CO
2
R2
Over the past decades, C-H bond functionalization has been
witnessed as one of the most efficient and straightforward
Buchner product
3
C(sp )-H
mixture)
2
C(sp
)-H
1
Metal: Rh, Fe, Ag, Cu,
(
synthetic strategy for constructing complex molecules. Given
b) & c) Our work: para-selective C-H functionalization
benzene derivatives widely existing in nature, site-selctive C-H bond
2
N
2
functionalization of arenes is is highly important. Transition-metal-
CO CH
2
2CF3
O
Ar
CO
2
CH
2
CF
3
R
R
catalyzed, chelate-assisted approach is widely explored and popular,
in which the presences of directing groups (DGs) lead to relatively
R
Ar1
Carbohydrates
Ar
O
b) Known
Ar2
3
-5
Ar1
easier selectivity control. However, compared to well-established
Au
Unknown
CO Me
2
2
3
ortho C(sp )-H functionalization and recently developed meta
H
c)
CO
2
R
Ph
2
4
R = alkyl
N
2
Ar1
C(sp )-H functionalization via the coordination between DGs and
Ar2
2
5
transition-metals, para-selective C(sp )-H bond functionalization is
2
CO R
CO R
2
IG
IG = hologen, alkynyl etc.
less explored and still long challenging especially for
FG
6
monosubstituted arenes without coordinating atom (e.g. N, O).
Scheme 1. The Reaction of monosubstituted arenes and diazo
The transition-metal-catalyzed carbene transfer reaction of diazo
compounds has emerged as a promissing approach to C−H bond
esters.
7
functionalization. The bond dissociation of carbon-hydrogen
Very recently, we have developed a novel and efficient gold-
2
3
2
energy of aromatic C(sp )-H higher than that of aliphatic C(sp )-H, catalyzed C(sp )-H functionalization of toluene with 2,2,2-
1
3e
especially the C-H bond being at benzylic position or adjacent trifluoroethyl α-aryl-α-diazoesters (Scheme 1b).
However, the
8
heteroatoms such as N or O. Thus, the chemo- and site-selectivity trifluoroethyl is necessary in this transformation, which limits the
are the most important issues in the C-H functionalization of utilization of this strategy in organic synthesis. Thus, the
9
3
2
arenes (Scheme 1a). For examples, the benzylic C(sp )-H development of alternative protocol to realize the C(sp )-H
functionalization of toluene have been reported by Che and Davies functionalization of toluene with the diazo esters with normal ester
9
a-b
10-12
via rhodium catalysis. Recently, gold
carbenes exhibited very group is highly desirable. As the design we proposed before, the
unique reactivity and selectivity compared to that of other noble key issue to realize this tranformation is installing the electron-
metals such as Rh, Cu, and Pd. With our continous interest in gold- withdrawing group (EWG) on ester group of diazoesters to enhance
2
13
catalyzed C(sp )-H functionalization of arenes with diazoesters, we the electrophilicity of the gold carbenes. We envisaged whether we
can also address this issue of the low reactivity of alkyl α-aryl-α-
diazoesters via installing an EWG on aryl as induced groups instead
of the trifluoromethyl on ester groups.
To test the feasibility of this hypothesis, our initial study was to
examine the reaction of α-(2-chloro)phenyl diazoacetate (2b) with
toluene 1a under the catalysis of different catalysts. The desired
para-selective C-H functionalization product 3aa was obtained in 56%
isolated yield when the reaction was catalyzed by (2,4-
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6
tBuC O)PAuPhCNSbF (Table 1, entry 1), which has shown high
Journal Name
6
H
3
2
performance in C(sp )-H functionalization of toluene with 2,2,2-
trifluoroethyl α-aryl-α-diazoesters. After further optimization of
gold catalysts (Table 1, entry 2-5), to our delight, the best result was
3
obtained and 3aa was isolated in 98% yield when Ph PAuOTf was
chosen as the catalyst (Table 1, entry 5). A series of other metal
catalysts, such as Rh, Ru, Cu, Fe et al. which are commonly used in
carbene transfer, were also tested, and diverse products via the
benzylic C-H insertion, cyclopropanation or Buchner reaction, ortho-
C-H functionalization, diazo’s coupling or mixture were detected
(Table 1, entries 6-8 and Table S1 in Supporting Information). It
should note that this protocol proceeds smoothly, even using only 2
equiv. of toluene in DCM (Table 1, entry 9). The structure of 3aa
1
4
was confirmed by single-crystal X-ray diffraction analysis.
a
Table 1. Optimization of reaction conditions.
Scheme 2. Scope with respect to various arenes.
b
entry
Ar (2)
catalyst
5 mol%)
yield (%)
(
3/4/5/6/7
1
2
3
4
5
6
2-ClC
2-ClC
2-ClC
2-ClC
2-ClC
2-ClC
2-ClC
2-ClC
2-ClC
6
H
5
(2a)
(2a)
(2a)
(2a)
(2a)
(2a)
(2a)
(2a))
(2a)
LAuPhCNSbF
LAuOTf
6
56/0/0/0/40
44/0/0/0/46
3/0/0/0/90
6
6
6
6
6
6
6
6
H
5
H
5
IPrAuOTf
H
5
JohnPhosAuOTf
PPh AuOTf
Rh(OAc)
5/0/0/0/89
H
5
3
(98)/0/0/0/(1)
0/0/(57)/0/(18)
15/4/9/43/0
0/0/0/56/34
(76)/0/0/0/(10)
H
5
2
c
7
H
5
Fe(OTf)
AgOTf
2
8
H
5
d
9
H
5
3
PPh AuOTf
a
Unless specific note, the solution of 2 (0.4 mmol) in 0.2 mL of toluene
was introduced into catalyst (5 mol%) in toluene (0.4 mL) at room
temperature by a syringe in 1 min and then being stirred for another 2
b
c
o
min. NMR yield. The number in parenthesis is isolated yield. 110 C.
d
t
2 2 2 6 3 3
Toluene (2 equiv.) was used in CH Cl (1 mL). L = (2,4- Bu C H O) P
The optimal reaction conditions were then utilized to the
reactions of a variety of benzene derivatives 1 and α-aryl
diazoesters 2 (Scheme 2). The reactions of arenes with different
Scheme 3. Scope with respect to diazo compounds.
We then investigated the scope of this gold-catalyzed highly site-
alkyl groups (1b-1m) and 2a were complete at room temperature in selective C−H bond funcꢀonalizaꢀon of toluene 1a by variation of
2
3
mins, affording the exclusive para C(sp )-H functionalization the component of α-aryl diazoesters 2. As shown in Scheme 3, the
products 3ba-3mm in good to excellent yields. It was noteworthy ethyl on the ester group of 2 has no effect on the yield and
3
that none of the products derived from C(sp )-H insertion or ortho, selectivity of the reaction (3ab), but the substituents with more
2
meta C(sp )-H functionalization was detected. To our delight, the steric hindrance (i-Pr or t-Bu) cause a little bit of yield decreasing
(
3ac-3ad). Those α-aryl α-diazoacetates with both strong and weak
arenes with heteroatoms attached to the alkyl substituent, such as
electron-withdrawing substituents on ortho position of the phenyl
ring (1e−1h) reacted smoothly with toluene to give the desired
products 3ae−3ah in good to excellent yields (82−91%, Scheme 2).
The strong electron-withdrawing substituents on para position
OTIPS groups are compatible in this transformation (3mm).
2
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were suitable for C-H bond functionalization of toluene (3ai−3aj, g of the corresponding product 3aa in 92% isolated yield (Scheme
Scheme 2). However, the weak electron-withdrawing groups at 4a). Most importantly, the activating halogen groups installed on
para position (1k) delivers the corresponding product 3ak in phenyl ring could be viewed as versatile functional groups for
relatively lower yield (45%), indicating the electron-withdrawing
ability of substituent on phenyl ring play a vital role in this
transformation. Those diazo esters with multiply electron-
withdrawing groups on phenyl ring showed high performance in
this C-H functionalization. Gratifyingly, the diazo esters installed
with menthol, glucose and a galactopyranoside reacted with
toluene smoothly, leading the para-selective C-H functionalization
product 3ao-3aq in excellent yield. These results indicate that this
protocol may be utilized to late-stage modification of natural
products or bioactive molecules.
further synthetic transformations. For example, the dechlorination
of 3aa led to the same C-H bond functionalization product from the
reaction of toluene and phenyl diazoester in 72% yield (Scheme 4b).
3
-aryl oxoindole 11, which moiety is widely found in natural
products and bioactive molecules, could be easily prepared from
aa via successive C-N coupling and amidation (Scheme 4c).
3
Transition-metal-catalyzed coupling reactions of 3af furnished
synthetic useful arylboron 12 and biphenyl 13 in 76% and 96% yield,
respectively (Scheme 4d and 4e).
In conclusion, we have established a novel and efficient gold-
catalysed cascade C-H functionzation of benzene derivatives with
alkyl α-aryl α-diazoesters in good to excellent yields with high
chemo- and site-selectivity. In this protocol, the electron-
withdrawing induced groups installed on phenyl group could
efficiently promote the chemo- and site-selective C-H bond
functionalization. Furthermore, the induced groups are versatile
functional groups for further synthetic transformations. Therefore,
we anticipate that this study will promote the utilization of metal-
carbene in more plentiful and novel C-H functionalization and
efficient organic synthesis.
It should note that o-alkynyl is also a good activating group for
this C-H bond functionalization of toluene. When o-alkynyl phenyl
diazoester 8 was subjected to the reaction under standard
conditions, the reactions proceeded smoothly, leading the
corresponding products 9a and 9h in good yields via the cascade C-
H functionzation/5-endo-dig carbocyclization (eqn (1)). To our best
knowledge, this is the first example of trapping the zwitterionic
intermediate from C-H bond functionalization of unactivated arenes.
We are grateful to National Natural Science Foundation of
China (21572065, 21425205, 21372084), the Shanghai Pujiang
Program (14PJ1403100), the 973 programs (2015CB856600),
Changjiang Scholars and Innovative Research Team in
University (PCSIRT) for financial supports.
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Scheme 4 Gram scaleup and the transformation of products 3aa
and 3af.
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2
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2
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(
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DOI: 10.1039/C7CC05649D
Journal Name
COMMUNICATION
O
Ar1
N
2
Carbohydrates
O
CO
2
R
Ar2
Ar1
R
IG
CO Me
2
CO
2
R
Ph
IG = hologen, alkynyl etc.
R
Ar1
Ar2
H
Au
CO R
R = alkyl
2
FG
A gold(I)-catalyzed cascade C-H functionalization of unactivated arenes with
been developed.
α-aryl
α-diazoesters with electron-withdrawing groups have
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