Tandem Thorpe Reaction/Palladium Catalyzed Asymmetric Allylic Alkylation: Access to Chiral β-enaminonitriles with Excellent Enantioselectivity

Article abstract of DOI:10.1002/asia.201601571

A new type of nucleophile, a 3-imino nitrile carbanion generated in situ by Thorpe reaction of acetonitrile with a base, was developed successfully and applied in a Pd-catalyzed asymmetric allylic alkylation with mono-substituted allyl reagents under Pd/S

Full text of DOI:10.1002/asia.201601571

CHEMISTRY
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Accepted Article
Title: Tandem Thorpe reaction/palladium catalyzed asymmetric allylic
alkylation: Access to chiral β-enaminonitriles with excellent
enantioselectivity
Authors: Xue Long Hou, Da-Chang Bai, Xiu-Yan Liu, Hao Li, and
Chang-Hua Ding
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COMMUNICATION
Tandem Thorpe reaction/palladium catalyzed asymmetric allylic
alkylation: Access to chiral β-enaminonitriles with excellent
enantioselectivity
[
a]
[a]
[a]
[a]
[a,b]
Da-Chang Bai, Xiu-Yan Liu, Hao Li, Chang-Hua Ding,* and Xue-Long Hou*
Abstract: A new type of nucleophile, 3-imino nitrile carbanion
generated in-situ by Thorpe reaction of acetonitrile with base, was
developed successfully and applied in Pd-catalyzed asymmetric
allylic alkylation with mono substituted allyl reagents under
Pd/SIOCPhox catalysis, affording β-enaminonitrile products in high
yields with excellent regio- and enantioselectivities.
group, a useful subunit in the synthesis of heterocycles and
[
8,9]
polymers as well as in pharmaceutical chemistry.
Obviously,
3a should be produced from the reaction of allyl reagent 1a with
nucleophile C, a new type of nucleophile formed in situ from two
molecules of acetonitrile by attack of α-carbanion of acetonitrile
A to another acetonitrile followed by isomerization (Scheme 1).
Base
N
CH3
N
CH2
N
CH2
Since its discovery in about 40 years ago, palladium-catalyzed
asymmetric allylic alkylation (AAA) has demonstrated its power
in enantioselective construction of carbon-carbon and carbon-
Pd2+Ln
?
CN
N
CH2
R
[
1]
hetero atom bonds as well as in organic synthesis. To date
many efforts have been paid to the development of new type of
A
R
L = SIOCPhox
2a
[
1-3]
nucleophiles including carbon nucleophiles.
Although α-
carbanions of ketones and carboxylic acid derivatives have
successfully been used as carbon nucleophile in Pd-catalyzed
NH
N
NH
N
N
N
CH2
NH
NC
NH
NC
[
2,4e-h,k,l]
CH3
AAA,
carbanion of nitriles in Pd-catalyzed AAA, probably due to the
hardness" of carbanion and its interconversion between the C-
few reports appeared regarding the use of α-
A
B
C
D
"
Pd2+Ln
[
3]
[5]
and N-metalated forms. Because of rich chemistry of nitriles
and importance of nitrogen-containing molecules in life science,
NC
Ph
NC
Ph
NC
NH2
[
6]
Ph
L = SIOCPhox
development of nitrile-containing carbanion as nucleophile in Pd-
catalyzed AAA is highly demands. We have been involved in Pd-
catalyzed AAA for years and developed some new types of
C
3a'
3a
Scheme 1. 3-Imino nitrile carbanion prepared in situ from acetonitrile
Table 1. Optimization of reaction parameters for Pd-catalyzed allylic alkylation
[
4]
nucleophiles. During the study on the use of “hard” carbanions
in the reaction, we found that a novel carbon-nucleophile, 3-
[a]
of 3-imino nitrile carbanion with allyl substrate 1
[
7]
imino nitrile carbanion, was formed and corresponding allylic
allylation products were afforded in excellent ee when using
acetonitrile in Pd-catalyzed AAA. In this communication, we
would report this tandem Thorpe reaction/Pd-catalyzed
asymmetric allylic alkylation of acetonitrile with mono substituted
allyl reagents, affording β-enaminonitrile products in high yields
with excellent regio- and enantioselectivities (Scheme 1).
[
8,9]
Despite the importance of this useful building block,
limited methods have been reported for their synthesis.
only
[
10]
At the beginning, we used acetonitrile to react with cinnamyl
phosphate 1a in the presence of Pd/SIOCPhox catalyst with
LHMDS as base to see if α-carbanion of acetonitrile was
produced and reacted as nucleophile. However, we could not
obtain the expected allylic alkylation product 2a, instead, we
separated allylated nitrile 3a, which contains β-enaminonitrile
[
b]
[c]
[c]
[d]
entry
L
solvent
THF
THF
THF
THF
THF
THF
THF
THF
Yield (%)
82
B/L
E/Z
ee (E/Z)(%)
85/91
55/60
-65/--
ND
1
2
3
4
5
6
L1
L4
L3
L2
L5
L6
L1
L1
97/3
91/9
90/10
91/9
97/3
93/7
95/5
36/64
89/11
89/11
88/12
88/12
89/11
85/15
89/11
--
78
[
[
a]
b]
D.-C. Bai, X.-Y. Liu, H. Li, Dr. C.-H. Ding, Prof. Dr. X.-L. Hou
State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy
of Sciences (CAS)
30
26
345 Lingling Road, Shanghai 200032, China
75
85/83
-24/0
E-mail: xlhou@sioc.ac.cn; dingch@sioc.ac.cn
Prof. X.-L. Hou
84
Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis,
SIOC, CAS
[
e]
7
51
73/--
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
[f]
8
40
33 /--
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COMMUNICATION
Table 2. Substrate scope of Pd-catalyzed allylic alkylation of 3-imino nitrile
carbanion with allyl substrate 1
9
1
1
1
1
1
1
1
1
1
1
2
L1
L1
L1
L1
L1
L7
L8
L9
L7
L7
L7
L7
DME
Et
73
89
72
95
NR
96
74
73
88
99
99
90
95/5
97/3
99/1
95/5
--
88/12
88/12
86/14
89/11
--
87/84
89/91
88/90
91/93
--
[a]
0
1
2
3
4
5
6
7
8
9
0
2
O
dioxane
toluene
2 2
CH Cl
toluene
toluene
toluene
toluene
toluene
toluene
toluene
96/4
95/5
95/5
96/4
98/2
96/4
>99/1
89/11
83/17
80/20
89/11
89/11
90/10
90/10
94/93
62/66
87/90
88/90
94/97
95/95
96/98
[
b]
[c]
[c]
ee (E/Z)
[d]
entry
R
yield (%)
B/L
E/Z
(
%)
[
e]
e]
1
2
3
4
5
6
7
8
9
Ph (1a)
3a, 90
3d, 94
3e, 94
3f, 73
3g, 99
3h, 99
3i, 81
3j, 88
3k, 90
3l, 98
3m, 81
NR
>99/1
95/5
>99/1
95/5
95/5
94/6
>99/1
99/1
>99/1
98/2
94/6
--
90/10
90/10
90/10
89/11
90/10
90/10
90/10
90/10
88/12
90/10
88/12
--
96/98
88/--
93/--
95/--
87/--
89/--
90/--
93/--
95/--
95/--
94/--
--
[
[
[
[
g]
h]
i]
[
4-MeC
6
H
4
(1d)
(1e)
i
4-PrC
6
H
4
4-FC
4-ClC
4-BrC
6 4
H (1f)
j]
6
H
4
(1g)
(1h)
3
[
a] Reaction conditions: 1a/LiHMDS/[Pd(η -C
mL CH CN, 0.2 mmol 1 in solvent (3.0 mL), CH
h, room temperature, monitored by TLC. [b] Isolated yield. [c] Determined by
H NMR. [d] Determined by HPLC. [e] 1b with OCO
used instead of 1a. [f] 1c with Cl as leaving group was used instead of 1a. [g]
3
H
5
)Cl]
2
/L = 100/125/2.5/6, 0.25
CN reacted with base for 1.5
6
H
4
3
3
1
4-CF C H (1i)
Me as leaving group was
3
6
4
2
o
o
[e]
0
C. [h] 40 C. [i] LiCl (1.0 equiv). [j] LiCl (1.0 equiv), CH
for 24 h at room temperature.
3
CN reacted with base
3-MeC
6
H
4
(1j)
(1k)
(1l)
3-MeOC
6 4
H
To understand better this tandem reaction and to improve its
efficiency, the influence of the reaction parameters on the
reaction was investigated. SIOCPhox ligands developed by us
were adopted as they showed excellent regio- and
enantioselectivities in the Pd-catalyzed AAA. When cinnamyl
10
2-MeC H
6 4
4
1
1
2
2-Naphthyl (1m)
Cyclohexyl (1n)
1
phosphate 1a was reacted with acetonitrile using LHMDS as
3
3
base in the presence of [Pd(η -C
3
H
5
)Cl]
2
and (S
c
a
,Rphos,R )-
3 5 2
[a] Reaction conditions: 1/LiHMDS/[Pd(η -C H )Cl] /L7 = 100/125/2.5/6, 0.25
o
3
mL CH CN, 0.2 mmol 1 in solvent (3.0 mL), 30 C. [b] Isolated yield. [c]
1
SIOCPhox (L1) in THF at room temperature, allylation product
Determined by H NMR. [d] Determined by HPLC. The ee of Z-product except
for 3a was not determined. [e] Room temperature.
3
8
a was obtained in 82% yield with B/L ratio of 97/3, E/Z ratio of
9/11, and ee of 85% for E isomer (Table 1, entry 1). The
evaluation of SIOCPhox ligands revealed the importance of their
structure in controlling the yield and enantioselectivities of the
product (Table 1, entries 1-6). The examination of leaving group
Under the optimized reaction conditions, the scope of the
substrates was examined (Table 2). The reaction proceeded
well for a wide range of cases, affording alkylation products in
73-99% yields with branched/linear ratio of 94/6-99/1, E/Z ratio
of 88/12-90/10 and 87-96% ee for (E)-products. In all cases
excellent regioselectivity was obtained. A little bit lower ee were
obtained for 3d and 3e with methyl- and isopropyl- on the para-
position of the phenyl ring (Table 2, entries 2 and 3). Fluoro,
chloro, bromo and trifluoromethyl at the para-position of the
phenyl ring were tolerated (Table 2, entries 4-7). The reaction
also worked well for allyl substrates 1 with m-methyl, m-methoxy,
and o-methyl as substituent on phenyl ring, affording allyl
products with excellent enantioselectivity (Table 2, entries 8-10).
The yield was slightly lower when 2-naphthyl allyl substrate 1m
was used (Table 2, entry 11). No desired product was obtained
when cyclohexyl allyl reagent 1n was used because β-H
elimination took place (Table 2, entry 12).
(
LG) of allyl substrate 1 showed that the phosphate ester was
best (Table 1, entry 1 vs entries7 and 8). The screen of solvent
effect indicated that toluene was the choice among tested
solvents since the reactivity and the enantioselectivity is better
than other solvents (Table 1, entry 1 vs entries 9-13). With
toluene as solvent, the substituent of oxazoline in SIOCPhox
ligand was examined (Table 1, entries 14-16). When the
c a
(S ,Rphos,R )-SIOCPhox (L7) with Ph as substituent was used,
the ee increased to 94% while the yield and the E/Z-selectivity
was maintained (Table 1, entry 14). When the reaction
o
temperature was 0 C , the ee of the major product decreased to
o
8
8% while it was 40 C, the ee of the major product was same
as that at room temperature (Table 1, entry 14 vs entries 17-18).
It was found that the use of LiCl as additive benefited the
reactivity and selectivity (Table 1, entry 19). When the reaction
time of CH CN with base was extended, the ee of the major
3
product increased to 96% with excellent regio- and E/Z-
It is known that various nucleophiles can be obtained with
different nitrile by Thorpe reaction, so we tried some other
nitriles in this Pd-catalyzed AAA. When acetonitrile and
benzonitrile were used in our system, only Thorpe reaction
occurred but no palladium catalyzed allylic alkylation product
selectivities (Table 1, entry 20).
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was obtained (eq 1), probably due to the steric hindrance of the
nucleophile generated by Thorpe reaction.
Trost, G. M. Schroeder, J. Am. Chem. Soc. 1999, 121, 6759; d) M.
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allylpalladium intermediate (eq 2). All of these results support
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[
1,11]
the proposed pathway depicted in Scheme 1.
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3]
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8
The absolute configuration of product 3h was assigned as
R) and the alkene configuration was determined as E by X-ray
analysis of its single crystal.
7
(
O. Tverskoy, G. Helmchen, Synlett 2008, 2803; Rh: k) P. A. Evans, S.
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[
12]
In summary, a new type of carbon-nucleophile has been
developed from the reaction of acetonitrile with base and used in
Pd-catalyzed AAA with monosubstituted allyl reagents
successfully, affording β-enaminonitrile products in high yields
with high regio- and enantioselectivities. These results not only
show the formation and application of new type of nucleophile in
Pd-catalyzed AAA but also provide some information, which
should be useful in the development of new type of nucleophile.
[
4]
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Acknowledgements
Financially supported by the National Natural Science
Foundation of China (NSFC) (21532010, 21372242, 21472214,
2
1421091), the NSFC and the Research Grants Council of Hong
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a) F. F. Fleming, L. Yao, P. C. Ravikumar, L. Funk, B. C. Shook, J.
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Keywords: palladium · allylic alkylation ·3-imino nitrile
·asymmetric catalysis ·Thorpe reaction
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Fleming, Nat. Prod. Rep.1999, 16, 597.
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1]
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For internal use, please do not delete. Submitted_Manuscript
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COMMUNICATION
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2
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[12] Crystallographic data of compound 3h have been deposited at the
Cambridge Crystallographic Data Centre with CCDC 1510786. For its
structural detail, see the Supporting Information.
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Chem. 1989, 26, 1575.
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COMMUNICATION
COMMUNICATION
Da-Chang Bai, Xiu-Yan Liu, Hao Li,
Chang-Hua Ding,* and Xue-Long Hou*
Page No. – Page No.
Tandem Thorpe reaction/palladium
catalyzed asymmetric allylic
alkylation: Access to chiral β-
enaminonitriles with excellent
enantioselectivity
Text for Table of Contents
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