Cu-Catalyzed highly selective reductive functionalization of 1,3-diene using H2O as a stoichiometric hydrogen atom donor

Article abstract of DOI:10.1039/c9cc04011k

A copper-catalyzed highly regio- A nd diastereo-selective reductive reaction of terminal 1,3-diene with water and aldehyde has been developed. This chemistry afforded a product containing a terminal alkenyl group, which is a versatile kind of precursor for organic synthesis, with the scope for various substrates. The present reaction system could realize the catalytic transfer of hydrogen to diene using water as a stoichiometric H atom donor. In this transformation, B₂Pin₂, a mild and practical kind of reductant was used as the mediator. The reaction pathway of this practical strategy was illustrated by a control experiment.

Full text of DOI:10.1039/c9cc04011k

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Cu-catalyzed highly selective reductive functionalization of 1,3-
diene using H2O as stoichiometric hydrogen atom donor
Qifan Li, a Xiaoyang Jiao, a Mimi Xing, a Penglin Zhang, a Qian Zhao a and Chun Zhang*ab
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A copper-catalyzed highly regio- and diastereo-selective reductive been extensively applied in such reaction, owing to the low
reaction of terminal 1,3-diene with water and aldehyde have been price of copper-catalysts, ambient reaction conditions or
developed. This chemistry afforded the terminal alkenyl group practical reaction protocols.4 With such powerful strategy,
containing product, which is a kind of versatile precursors for terminal diene could be converted into 1,4- or 3,4-
organic synthesis, with various substrate scopes. The present functionalized product with good selectivity (1, Scheme 1).
reaction system could realize catalytic transfer hydrogen to diene Comparing with above synthetic strategy, we developed a
using water as
a stoichiometric H atom donor. In this novel copper-catalyzed B2Pin2 mediated highly regio- and
transformation, B2Pin2, a kind of mild and practical reductant was diastereo-selective functionalization of terminal 1,3-diene to
used as the mediator. The reaction pathway of this practical afford 1,2-functionalized product (2, Scheme 1).
strategy was illustrated by control experiment.
Table 1. The effect of different reaction conditions. a
H
Develop new organic transform strategy to reserve active
[Cu] (10 mol%), PPh3 (11 mol%)
function group is important for the synthesis of drug, nature
Ph
+
Ph
Ph
O
Base (2.0 equiv), B2Pin2 (2.0 equiv)
product and functional material molecule.1 Among a lot of
versatile starting compounds, 1,3-diene has caught more and
more attention, because difunctionalization of conjugated
diene with high regio- and diastereo-selectivity is an important
class of transformation, which could control the formation of
multiple complex isomeric product from simple precursor.2,3 In
recent several years, copper-catalyzed reaction systems have
1a
2a
HO
Ph
3aa
H O
(3.0 equiv), solvent (1.5 mL), N2
2
[Cu]
entry
solvent
THF
base
yield (%)b
dr
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
1
2
3
4
5
6
LiOt-Bu
NaOt-Bu
KOt-Bu
LiOMe
76
52
69
66
64
80
5:1
4:1
5:1
2:1
4:1
9:1
THF
THF
THF
1.4-dioxane
LiOt-Bu
LiOt-Bu
Scheme 1. Functionalization of terminal 1,3-diene.
1). Previous work: Cu-catalized functionalization of terminal 1,3-diene to make
3,4-product and 1,4-product
toluene
DCE
DCE
DCE
DCE
DCE
DCE
R2
Cu(OTf)2
7
LiOt-Bu
LiOt-Bu
LiOt-Bu
LiOt-Bu
LiOt-Bu
LiOt-Bu
93
76
78
23
0
>20:1
>20:1
>20:1
13:1
--
R2
C3
R
[Cu]
conditions
R1
R
R1
R
2
+
X
R1+
+
R
X
C4
C2
Cu(acac)2
8
C1
9
CuCl
3,4-product
1,4-product
10
11c
12
CuOAc
Cu(OTf)2
2). This work: The strategy to make terminal alkenyl group reserved product
HO
R2
C3
[Cu], B2Pin2
conditions
R1
C1
H
none
0
--
R2
H
2O
+
+
O
R
C4
C2
a 1a (0.25 mmol), 2a (0.5 mmol), B2Pin2 (0.5 mmol), base (0.5 mmol), cat (10 mol
b
%), PPh3 (11 mol%), H2O (3.0 equiv), solvent (1.5 ml).
Isolated yield,
1,2-product
diastereomers are inseparable, dr was determined by 1H-NMR. c Without B2Pin2.
Contrasted to other metal reagents, the organic boron-
reagent is much more stable, ambient and practical, so
preparation of this kind of compound has been studied
intensely.5 Among them, hydroboration of dienes could afford
the important boron reagent, which is a kind of powerful
intermediate for a lot of transformation.6 However, some air
or moisture sensitive reagents and catalysts, such as Ni(cod)2
a. Department of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic
Science, School of Sciences, Institute of Molecular Plus, Tianjin University, Weijin
Rd. 92, Tianjin 300072, China.
b. State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin
300071, China
†
Electronic
Supplementary
Information
(ESI)
available:
See
DOI: 10.1039/x0xx00000x
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and HBPin, were usually used for those reactions. The present the result of this reaction (entry 8 to 10, TablVeiew1)A.rticAlemOonlninge
DOI: 10.1039/C9CC04011K
transformation could construct allyl boron intermediate with them, Cu(OTf)2 was the best choice. The data of entry 11 and
good regioselectivity by the copper-salt/H2O/B2Pin2 system, 12 proved this reaction did not work without copper catalyst
which made this method more practical. Importantly, the or B2Pin2 (Table 1).
examples of catalytic transfer hydrogenations of simple
alkenes using H2O as the stoichiometric H atom donor is the Table 3. Cu-catalyzed B2Pin2 mediated reductive reaction of 1a
sustainable strategy for organic synthesis.7 Our work exploits a with different aldehyde (2).a
H
new way via using H2O as the safe and cost benefit hydrogen
atom source for highly selective catalytic reductive
transformation process.
Cu(OTf)2 (10 mol%), PPh3 (11 mol%)
LiOtBu (2.0 equiv), B2Pin2 (2.0 equiv)
Ph
HO
R2
+
O
Ph
(3.0 equiv), DCE, 70 oC, N2
H O
2
R2
1a
2
3b
: yield%, dr
Our study commenced with the copper-catalyzed reaction of
(E)-buta-1,3-dien-1-ylbenzene (1a), benzaldehyde (2a), B2Pin2
and H2O. Interestingly, this practical one pot reaction afforded
2-benzyl-1-phenylbut-3-en-1-ol (3aa) with 76% yield and 5:1
diastereoselectivity (entry 1, Table 1 and SI). The efficiency of
this reaction was decreased by using other kinds of bases, such
as NaOt-Bu, KOt-Bu, or LiOMe (entries 1-4, Table 1 and SI). We
then surveyed the effect of different solvents. Compared with
THF, 1,4-dioxane induced low yield and selectivity, but toluene
and DCE afforded much better results (entry 5 to 7, Table 1).
Especially, when DCE was chosen as solvent, the product could
be given with 93% yield and better than 20:1
diastereoselectivity (entry 7, Table 1). Further studies
indicated different kinds of copper-salts could affect
Ph
HO
Ph
Ph
HO
Me
HO
Me
3aa
: 93%, >20:1
3ab
3ac
: 93%, >20:1
: 91%, >20:1
Ph
Ph
Ph
Ph
HO
HO
HO
CO2Me
: 91%, >20:1
CF3
: 95%, >20:1
Me
: 94%, >20:1
3ad
3ae
3af
Ph
HO
Ph
HO
O
HO
Me
O
Me
N
Me
: 81%, >20:1
OMe
: 89%, >20:1
OMe
: 86%, >20:1
3ag
3ah
Ph
3ai
Ph
HO
Ph
HO
Table 2. Cu-catalyzed B2Pin2 mediated reductive reaction of 2a
with different terminal 1,3-diene (1).a
Cl
Cl
HO
H
Cl
Br
Cu(OTf)2 (10 mol%), PPh3 (11 mol%)
LiOtBu (2.0 equiv), B2Pin2 (2.0 equiv)
3aj
: 97%, >20:1
3ak
3al
: 91%, >20:1
: 87%, >20:1
R1
R1
+
Ph
O
(3.0 equiv), DCE, 70 oC, N2
H O
2
Ph
Ph
HO
HO
Ph
Ph
HO
3b
1
2a
Ph
: yield%, dr
O
F
O
O
HO
HO
Ph
F
HO
Ph
HO
I
3am
3an
3ao
: 81%, >20:1
: 94%, >20:1
: 68%, >20:1
Me
3ca
Me
3ba
3aa
: 93%, >20:1
: 88%, >20:1
HO
: 78%, >20:1
HO
Ph
Ph
Ph
Me
HO
Ph
MeO
Ph
Me2N
HO
HO
3aq
Ph
3ap
: 79%, 8:1
: 80%, 7:1
3da
3ga
3ea
3fa
: 69%, >20:1
: 51%, >20:1
: 78%, >20:1
Ph
Ph
F
HO
Ph
F3C
HO
Ph
Cl
HO
Ph
HO
3ar
Me
HO
3as
Cl
: 78%, 8:1
: 79%, 9:1
3ha
3ia
3la
: 83%, >20:1
: 77%, 16:1
: 82%, >20:1
a Standard reaction conditions: 1a (0.25 mmol), 2 (0.5 mmol), B2Pin2 (0.5 mmol),
Br
HO
Ph
I
HO
Ph
HO
Ph
LiOt-Bu (0.5 mmol), Cu(OTf)2 (10 mol%), PPh3 (11 mol%), H2O (3.0 equiv),
DCE (1.5 ml), 70 oC, under N2 condition. Isolated yield, diastereomers are
b
inseparable, dr was determined by 1H-NMR.
3ja
3ka
: 78%, 18:1
: 95%, >20:1
: 88%, >20:1
Using H2O as hydrogen atom donor and B2Pin2 as mediator
for this reductive transformation, the substrate scope of
terminal 1,3-diene was investigated (Table 2). In general,
modest to good yields and diastereoselectivity using either
electron-rich (MeO- and Me2N-), or electron-deficient (F-, CF3-
and Cl-) aryl substituted 1,3-diene were observed (3aa to 3ka,
table 2). And the substituents at ortho-position positions of the
arene group did not affect the efficiency (3ba, table 2).
Notably, when bromo-substituted aromatic 1,3-diene was
employed as substrate, the corresponding product could be
afforded with 95% yield and great selectivity, which could be
used for further transformation (3ja, Table 2). The iodo-
HO
Ph
HO
Ph
Ph
S
HO
Ph
O
3ma
3na
: 80%, 13:1
3oa
: 43%, 6:1
: 61%, 14:1
Me
H
Me
Me
HO
Ph
HO
Ph
Ph
H
HO
3pa
: 41%, 7:1
3qa
: 45%, 7:1
3ra
: 49%, >20:1
a Standard Reaction Conditions: 1 (0.25 mmol), 2a (0.5 mmol), B2Pin2 (0.5 mmol),
LiOt-Bu (0.5 mmol), Cu(OTf)2 (10 mol%), PPh3 (11 mol%), H2O (3.0 equiv), DCE
(1.5 ml), 70 oC, under N2 condition. b Isolated yield, diastereomers are inseparable,
dr was determined by 1H-NMR.
2 | J. Name., 2012, 00, 1-3
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substituted aromatic 1,3-diene still worked, but with lower scheme 2, the product 3aa could go throughVieewpAorxticidleaOtniloinne
10
efficiency (3ka, Table 2). To our delight, the naphthyl, furyl and reaction,8 Heck reaction,9 hydroboration-oxidation reaction
DOI: 10.1039/C9CC04011K
thienyl group could be survival under this reductive reaction and radical coupling reaction11 to afford the desired complex
condition (3la to 3na, Table 2). Importantly, alkyl 1,3-diene products smoothly (b, c, d and e, Scheme 2).
could be transfered into the corresponding products smoothly
(3oa to 3ra, table 2). The 1,2-disubstituted 1,3-diene still Scheme 3. Control experiments
worked well, which gave the quaternary carbon atom
containing product (3ra, table 2).
[Cu] and B2Pin2
(eq. 1)
(eq. 2)
Ph
Ph
BPin
: 96 % yield
Standard Conditions
1a
8
The substrate scope of the Cu-catalyzed B2Pin2 mediated
highly selective reductive transformation was further
expanded to a variety of substituted aldehydes (2) (Table 3).
These results indicated that aryl aldehyde with both electron-
donating and electron-withdrawing groups proceeded well
with good yields and great diastereoselectivity (3aa to 3ap,
Table 3). The substrate group at para-, meta-, and ortho-
position of arene ring did not affect the efficiency (3ab to 3ad,
Table 3). Notably, even when bromo-substituted or iodo-
substituted arylaldehyde was employed as starting material,
good results were afforded (3ak and 3am, Table 3). These
products could be used for further coupling reaction to make
complicated molecules. Moreover, under this ambient
reaction condition, the substrates with hetero-cycle groups
could be converted into desired products with good efficiency,
which exhibited the good substrate tolerance of this method
(3an and 3ao, Table 3). Furthermore, the substrate scope
could expand to alkyl aldehydes which afforded good yields
and moderate diastereoselectivity (3ap to 3as, table 3).
Ph
HO
Standard Conditions
Ph
+
+
Ph
Ph
O
O
Without 1a
PinB
Ph
8
2a
2a
3aa
:78% yield, 8:1 dr
D
Standard Conditions
Ph
Ph
(eq. 3)
D O
(3.0 eq)
2
1a
HO
Ph
: 92% yield,
3aa-D
>20:1 dr; d% = 71%
Ph
Standard Conditions
3aa
+
(eq. 4)
(eq. 5)
Ph
Ph
Ph
O
O
HO
Ph
2a
2a
1a-mix
: 84% yield, >20:1 dr
Z:E = 1.3:1
Ph
Standard Conditions
1a
Ph
+
Without
Without [Cu]
PinB
HO
Ph
8
3aa
:72% yield, >20:1 dr
To investigate the mechanism of this transformation, the
control experiments were designed. Firstly, without
benzaldehyde (2a), compound 8 could be separated with 96%
yield (eq. 1, Scheme 3). This result suggested 8 should be the
key intermediate of the present transformation. Furthermore,
when it was put into the similar standard conditions, the
desired product 3aa was afforded with good yield (eq. 2,
Scheme 3). A slight difference of the reaction system might
affect the diastereoselectivity and yield, which exhibited the
advantage of this one pot reaction strategy. The reaction of 1a
and 2a was tested in the presence of D2O, the D-labeled
product could be detected (eq. 3, Scheme 3). This result could
prove H2O is the stoichiometric H atom donor of Cu-catalyzed
B2Pin2 mediated highly selective reductive transformation.
Importantly, when Z and E version mixed buta-1,3-dien-1-
ylbenzene was selected as starting material, this chemistry
afforded as similar result as the example of 3aa from table 1
(eq. 4, Scheme 3). This data suggested the isomerization
process of allyl copper intermediate could be involved in this
transformation. Furthermore, without copper-catalyst, 8
react with 2a could afford 3aa with good yield and
diastereoselectivity (eq. 5, Scheme 3). This result suggested
copper did not participate in this step of the reaction.
Scheme 2. Large scale reaction and further transformation of
product.
O
Ph
4b
HO
Ph
Ph
m
8
Ph
HO
3
-
C
%
P
d
B
Ph
,
N
r
A
5c
:
3
t3
E
:
)2
%
,
1
c
I
-
A
h
O
P
(
d
P
0
7
Ph
1a
Ph
gram-scale
(11.5 mmol)
+
Ph
HO
3aa
Ph
2.0 g
75 % (
)
1
2a
>20:1 dr a
O
)
B
2
H
)
.
N
3
A
a
S
t
O
T
M
e
E
2
H
D
6
,
2
0
H
E
O
%
2
O
M
C
2
%
P
3
OH
F
,
4
I
Ph
HO
C
u
r
C
B
Ph
6d
CF2CO2Et
Ph
7e
HO
Ph
a 1a (11.5 mmol), 2a (23 mmol), B2Pin2 (23 mmol), LiOt-Bu (23 mmol), PPh3 (11
b
mol%), Cu(OTf)2 (10 mol%), DCE (69 ml), isolated yield. 3aa (0.25 mmol), m-
CPBA (0.375 mmol), DCM(1.3 ml), isolated yield. c 3aa (0.185 mmol), Ph-I (0.37
mmol), Pd(OAc)2 (10 mol%), Et3N (1.85 mmol), CH3CN (1.8 ml), isolated yield. d
.
3aa (0.2 mmol), BH3 SMe2 (0.6 mmol), NaOH (0.9 mmol), H2O2 (1.2 mmol), THF
e
(2.0 ml), isolated yield. 3aa (0.2 mmol), BrCF2CO2Et (0.3 mmol), CuI (10
Scheme 4. The proposed reaction mechanisum.
mol%), PMDETA (0.3 mmol), CH3CN (1.0 ml), isolated yield.
Ph
HO
[Cu] and B2Pin2
+
Ph
To test the feasibility of a large-scale reaction, the reaction
of (E)-buta-1,3-dien-1-ylbenzene (1a) (11.5 mmol) and
benzaldehyde (2a) (23 mmol) was investigated. The reaction
O
Ph
Standard Reaction Conditions
1a
2a
Ph
3aa
[Cu] B2Pin2
Cu
Ph
O
could afford 2.0
g
3aa (75% yield) with great
2a
diastereoselectivity (a, Scheme 2). The product of this
chemistry, which installed terminal alkenyl group, is a kind of
versatile intermediate for chemical synthesis. As shown in
BPin
H2O
[Cu]
Cu
BPin
Ph
BPin
Ph
Ph
9
10
8
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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On the basis of the above control experiments, a proposed
mechanism for the high selective reductive reaction was
illustrated in Scheme 4. The first step of this reaction was the
formation of the tautomer copper complex 9 and 10.4c, 4f, 12
The intermediate 10 reacted with water to give the
intermediate 8, which have been proved by the control
experiment.4f Further reaction of 8 with benzaldehyde (2a)
afforded the product 3aa.13
In summary, we have demonstrated a novel Cu-catalyzed
B2Pin2 mediate highly selective reductive functionalization of
1,3-diene using H2O as hydrogen donor. This practical
chemistry could afford the terminal alkenyl group containing
product with various substrate scopes, which is a kind of useful
block for organic synthesis. Furthermore, this method could
4
support
gram-scale
preparation
without
diminish
diastereoselectivity. Further studies for synthetic applications
are ongoing in our laboratory.
We acknowledge financial support from Tianjin University,
National Science Foundation of China (No. 21801181), “1000-
Youth Talents Plan” and State Key Laboratory of Elemento-
Organic Chemistry (Nankai University). We acknowledge Prof.
Ning Jiao (Peking University), Prof. Zhuangzhi Shi (Nanjing
University) and Prof. Jun-An Ma (Tianjin University) for helpful
discussion.
5
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Conflicts of interest
The authors declare no competing financial interest.
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