Chelation versus Non-Chelation Control in the Stereoselective Alkenyl sp2 C?H Bond Functionalization Reaction

Article abstract of DOI:10.1002/anie.201700559

A hydroxy group chelation-assisted stereospecific oxidative cross-coupling reaction between alkenes was developed under mild reaction conditions. In the presence of palladium catalyst, the alkenes tethered with hydroxy functionality can couple efficiently with electron-deficient alkenes to form the corresponding multi-substituted olefin products. The hydroxy group on the substrate could play dual roles in reaction, acting as the directing group for alkenyl C?H bond activation and controlling the stereoselectivity of the products.

Full text of DOI:10.1002/anie.201700559

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201700559
German Edition: DOI: 10.1002/ange.201700559
À
C H Alkenylation
Chelation versus Non-Chelation Control in the Stereoselective Alkenyl
2
À
sp C H Bond Functionalization Reaction
Qiu-Ju Liang, Chao Yang, Fei-Fan Meng, Bing Jiang, Yun-He Xu,* and Teck-Peng Loh*
Abstract: A hydroxy group chelation-assisted stereospecific
oxidative cross-coupling reaction between alkenes was devel-
oped under mild reaction conditions. In the presence of
palladium catalyst, the alkenes tethered with hydroxy function-
ality can couple efficiently with electron-deficient alkenes to
form the corresponding multi-substituted olefin products. The
hydroxy group on the substrate could play dual roles in
À
reaction, acting as the directing group for alkenyl C H bond
activation and controlling the stereoselectivity of the products.
O
lefins are a very important class of compounds in organic
chemistry. Accordingly, it is not surprising that many methods,
including the highly stereoselective methods, have been
developed towards their synthesis.[1] Among them, the
Wittig reactions,[2] transition metal-catalyzed cross-coupling
reactions,[3] and olefin methathesis[4] represent the most
commonly used approaches. Unfortunately, these methods
still suffer from poor atom economy, poor selectivities with
highly substituted alkenes, high cost of starting materials, and/
or the need to use expensive metal catalyst. Therefore, novel
and highly atom-economical method for the stereoselective
synthesis of alkenes utilizing cheap and easily available
starting materials that is amenable to large scale production
is highly desirable.[5] An attractive strategy to overcome these
Scheme 1. Palladium-catalyzed oxidative cross-coupling between
alkenes.
À
a selective alkenyl C H bond functionalization and tandem
cross-coupling reaction. Herein, we report for the first time
À
the realization of this concept for direct site-selective C H
bond functionalization and the tandem coupling reaction.
This method provides easy and practical access to highly
substituted alkenes with very high stereoselectivities.
To test the feasibility of this concept, we commenced the
hypothesized coupling reaction using homoallylic alcohol 1a
as the model substrate to couple with n-butyl acrylate in the
presence of palladium catalyst. It has been well established
that the combined catalytic system of palladium catalyst with
limitations is to develop transition-metal-catalyzed selective
sp2 alkenyl C H bond coupling reactions. While the
[6]
À
2
À
À
(hetero)aryl sp C H bond using transition-metal catalysts
amino acid ligand could mediate efficient direct C H bond
have witnessed significant progress in recent years,[7] stereo-
functionalization.[11] Therefore, we tested our model reaction
with this established procedure.
2
À
À
selective C H bond functionalization of alkenyl sp C H
bond remains elusive.[8] We envisage that the selective C H
Gratifyingly, the desired product 3a could be obtained in
59% yield with 84:16 (Z/E) stereoselectivity when 10 mol%
of Pd(OAc)2 and 50 mol% of N-acetyl-l-valine[12] were used
in the presence of 1.5 equiv Ag2CO3 as oxidant (Table 1,
entry 1). Furthermore, various amino acids were added to this
reaction, it was encouraging to find that N-acetyl-l-phenyl-
alanine could provide 76% (1H NMR yield) of product in
dioxane (Table 1, entry 5). Control experiments carried out
has validated the mandatory presence of palladium catalyst,
silver oxidant, ligand, and base to furnish the cross-coupling
product.
Under the optimized reaction conditions, we turned our
attention to explore the substrate scope of the olefinic
coupling partners (Scheme 2). As expected, good stereose-
lectivities of the products could be obtained when different
acrylates were coupled with alkene 1a. It is noteworthy that
the vinyltrimethylsilane was also an effective substrate for the
coupling reaction with 1a albeit in moderate yield of 48%.[13]
When other carbonyl derivatives such as ethyl vinylketone,
acroleine, and N,N-dimethylacrylamide were examined for
their compatibility as coupling partners in this reaction, the
À
bond functionalization of cheap and commercially available
homoallylic or allylic alcohols could be attained by judicious
choice of reaction conditions (Scheme 1).[9] Although this
chelation versus non-chelation concept has been used widely
in asymmetric synthesis,[10] it has never been utilized for
[*] Q.-J. Liang, C. Yang, F.-F. Meng, B. Jiang, Prof. Dr. Y.-H. Xu,
Prof. Dr. T. P. Loh
Department of Chemistry
University of Science and Technology of China
96 Jinzhai Road, Hefei, Anhui 230026 (China)
E-mail: xyh0709@ustc.edu.cn
teckpeng@ustc.edu.cn
Prof. Dr. T. P. Loh
Institute of Advanced Synthesis, Jiangsu National Synergetic Inno-
vation Center for Advanced Materials, Nanjing Tech University
30 South Puzhu Road Nanjing, Jiangsu 210009 (China)
and
Division of Chemistry and Biological Chemistry, School of Physical
and Mathematical Sciences, Nanyang Technological University
Singapore 637616 (Singapore)
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Table 1: Optimization of reaction conditions.[a]
were summarized in Scheme 3. It was found that the
corresponding products could be generated with good ste-
reoselectivities and in reasonable yields when different
functionalized alkyl-substituted homoallylic alcohols were
subjected to the reactions. Furthermore, reactions of various
3-aryl-substituted homollylic alcohols with 2a were exam-
ined. Both electron-donating and electron-withdrawing sub-
stituents on the phenyl ring could be well tolerated to afford
the desired products in good yields in most cases with high
stereoselectivities. Moreover, the hydroxy group and the
acrylate fragment were observed to retain at the same side in
the dominant stereoisomers of the cross-coupled products.
Entry Ligand
Additive Alcohol
Solvent
Yield[b] Z:E
1
2
3
4
Ac-Val-OH Cs2CO3 CF3CH2OH THF
Ac-Leu-OH Cs2CO3 CF3CH2OH THF
Boc-Val-OH Cs2CO3 CF3CH2OH THF
Ac-Phe-OH Cs2CO3 CF3CH2OH THF
59%
61%
29%
75%
84:16
83:17
50:50
81:19
5
Ac-Phe-OH Cs2CO3 CF3CH2OH 1,4-dioxane 76%[e] 88:12
6[c]
7[d]
8
Ac-Phe-OH Cs2CO3 CF3CH2OH 1,4-dioxane N.R.
Ac-Phe-OH Cs2CO3 CF3CH2OH 1,4-dioxane 4%
–
90:10
–
–
–
Cs2CO3 CF3CH2OH 1,4-dioxane N.R.
CF3CH2OH 1,4-dioxane trace
1,4-dioxane 40%
9
10
Ac-Phe-OH
Ac-Phe-OH Cs2CO3
–
–
88:12
[a] Reaction conditions: 1a (0.3 mmol), 2a (0.6 mmol), oxidant Ag2CO3
(1.5 equiv), additive (30 mol%), alcohol (5.0 equiv), and solvent
(0.6 mL) were added to a mixture of catalyst Pd(OAc)2 (10% mmol) and
ligand (50 mol%) and allowed to stir for 48 h under air atmosphere.
[b] Yield was determined by 1H NMR spectroscopy using mesitylene as
the internal standard. N.R.=no reaction. [c] No Pd(OAc)2. [d] No
Ag2CO3. [e] Isolated yield is 71%.
Scheme 2. Reactions of hydroxy group-tethered alkene 1a with elec-
tron-deficient alkenes. Reaction conditions: 1a (0.3 mmol), 2
(0.6 mmol), Pd(OAc)2 (10 mol%), Ac-Phe-OH (50 mol%), Cs2CO3
(30 mol%), CF3CH2OH (5.0 equiv) and Ag2CO3 (1.5 equiv) in 0.6 mL
1,4-dioxane at 508C under air atmosphere for 48 hours. Yields are of
isolated products. [a] Using THF as the solvent.
Scheme 3. Reactions of n-butyl acrylate with homoallylic alcohols.
Reaction conditions: 1 (0.3 mmol), 2a (0.6 mmol), Pd(OAc)2
(10 mol%), Ac-Phe-OH (50 mol%), Cs2CO3 (30 mol%), CF3CH2OH
(5.0 equiv) and Ag2CO3 (1.5 equiv) in 0.6 mL 1,4-dioxane at 508C
under air atmosphere for 48 hours. Yields are of isolated product; E-
and Z-products are named according to the Cahn–Ingold–Prelog
priority rules. [a] 3p’ is another coupling product along with 3p.
corresponding products were obtained in moderate to good
yields and/or with moderate to good stereoselectivities.
With n-butyl acrylate, various homoallylic alcohols were
applied for this reaction procedure, and the coupling results
2
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Finally, when the secondary and tertiary homollylic alcohols
respectively in the presence of 10 mol% of Pd(OAc)2 catalyst.
were subjected to this reaction, it was found that the expected
products could be obtained in moderate yields and good
stereoselectivities. When the structurally unmodified 3-buten-
1-ol was used to react with n-butyl acrylate, the desired
product 3ad was only obtained in low yield and with 68:32
(Z:E) stereoselectivity.
To explore the possible coordinating effect of hydroxy
group during this coupling process, allylic alcohol 1ab,
homoallylic 1q and 4-phenylpent-4-en-1-ol 1ac were individ-
ually reacted with n-butyl acrylate under the optimized
reaction conditions. The results showed that all substrates
could be transformed to the desired products with good
stereoselectivities but only homoallylic alcohol 1q afforded
the product in good yield (Scheme 4, Eqs. (1)–(3)). When the
homoallylic alcohol 1a was protected with different moieties
and subjected to this coupling reaction under the same
reaction conditions, neither the yield nor the stereoselectivity
of the corresponding product were satisfactory (Scheme 4,
Eq. (4)). On the basis of these results, a six-membered cyclic
The kinetic isotopic effect value (KIE) of 2.02 could be
determined from their initial rate ratios (Scheme 5, Eqs. (5),
(6); for details see the Supporting Information). Moreover,
the kinetic study to investigate the effect of the palladium
catalyst was performed. A first-order dependence of initial
rate on the amount of Pd(OAc)2 was observed (Figure 1, see
the details in the Supporting Information). These results
À
suggest that the C H bond cleavage could be the possible
rate-determining step in this coupling reaction.[14]
À
palladium species generated from alkenyl C H bond activa-
tion and coordination of hydroxy group could be proposed as
the possible intermediate.
Scheme 5. Kinetic isotope effect determined from 1q/1q’.
To gain further insights into mechanistic pathway of
current coupling reaction, reactions of 1q and its di-deuter-
ated analogue 1q’ with n-butyl acrylate were carried out,
Figure 1. A first-order dependence of initial rate on the amount of
Pd(OAc)2.
Based on the above results, a plausible mechanism for the
current coupling reaction is proposed as shown in
Scheme 6.[15] Firstly, with the chelation of hydroxy group,
À
the palladium can activate the alkenyl C H bond and form
a six-membered palladium species A. Following the coordi-
nation and migratory insertion of the n-butyl acrylate, the
intermediate C can be generated. This will then lead to the
formation of the product whereby the Pd0 generated can be
re-oxidized into PdII with the aid of silver oxidant.
In conclusion, a palladium-catalyzed oxidative cross-
coupling reaction between homoallylic alcohols and elec-
tron-deficient alkenes has been developed. With the judicious
choice of the hydroxy-bearing alkenes, highly stereoselective
synthesis of alkenes can be obtained.
Scheme 4. [a] Reaction conditions: 4 (0.3 mmol), 2a (0.6 mmol),
Ag2CO3 (1.5 equiv), Cs2CO3 (30 mol%), CF3CH2OH (5.0 equiv), and
1,4-dioxane (0.6 mL) were added to a mixture of catalyst Pd(OAc)2
(10% mmol), ligand (50 mol%) and allowed to stir for 48 h under air
atmosphere. [b] Yield of isolated product. [c] Selectivity was deter-
mined by 1H NMR spectroscopy.
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Scheme 6. Proposed plausible mechanism for the palladium-catalyzed
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Acknowledgements
We gratefully acknowledge the funding support of the
National Natural Science Foundation of China (21372210,
21672198) and the State Key Program of National Natural
Science Foundation of China (21432009). We appreciate the
assistance of Jun Kee Cheng for her draft polishing work.
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Conflict of interest
The authors declare no conflict of interest.
À
Keywords: alkenylation · C H activation · cross-coupling ·
palladium
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Manuscript received: January 17, 2017
Final Article published: && &&, &&&&
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À
C H Alkenylation
Q.-J. Liang, C. Yang, F.-F. Meng, B. Jiang,
Y.-H. Xu,* T. P. Loh*
&&&& — &&&&
Chelation versus Non-Chelation Control
Stereospecific oxidative cross-coupling
between alkenes assisted by hydroxy
group chelation was developed. In the
presence of palladium catalyst, alkenes
tethered by the hydroxy functionality can
couple with electron-deficient alkenes to
form olefin products. The hydroxy group
acts as both directing group for alkenyl
2
À
in the Stereoselective Alkenyl sp C H
Bond Functionalization Reaction
À
C H bond activation and stereoselectiv-
ity control.
6
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Angew. Chem. Int. Ed. 2017, 56, 1 – 6
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