Nickel-catalyzed synthesis of (E)-olefins from benzylic alcohol derivatives and arylacetonitriles via C-O activation

Article abstract of DOI:10.1039/c5cc10005d

An efficient Ni-catalyzed synthesis of (E)-olefins using the readily available benzylic alcohol derivatives and arylacetonitriles is described. This transformation should proceed via a tandem process involving nickel-catalyzed cross coupling via C-O activation and subsequent stereoselective E2 elimination.

Full text of DOI:10.1039/c5cc10005d

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DOI: 10.1039/C5CC10005D
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Nickel-Catalyzed Synthesis of (E)-Olefins from Benzylic Alcohol
Derivatives and Arylacetonitriles via C-O Activation
Jing Xiao,a Jia Yang,a Tieqiao Chen,*a and Li-Biao Han*b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
An efficient Ni-catalyzed synthesis of (E)-olefins using the readily Thus, despite the great progress has been made in this filed,
available benzylic alcohol derivatives and arylacetonitriles is continuous efforts still deserve for developing facile and
described. This transformation should proceed via a tandem efficient methods for the preparation of olefins from simple
process involving nickel-catalyzed cross coupling via C-O activation starting materials. Herein, we report a Ni-catalyzed tandem
and subsequent stereoselective E2 elimination.
reaction for the selective synthesis of (E)-olefins using the
Table 1 Ni-catalysed synthesis of 2-styrylnaphthalene from 2-
The stereoselective synthesis of olefins is of importance in
organic synthesis, because many functional molecules such as
materials, drugs, natural products incorporate carbon-carbon
double bonds with defined (Z) or (E)-configuration.1 Classical
methods to access olefins include the popular Wittig reaction
and Julia olefination, which depend on the transformation of
carbonyl compounds with phosphonium salts or sulfone
compounds.2 Alternatively, many transition metal-catalyzed
methodologies based on alkenes such as metathesis, Mizoroki-
Heck couplings (reactions of organohalides or counterparts
with terminal alkenes) and Fujiwara-Moritani couplings
(reactions of electron-rich hydrocarbons with electron-
deficient terminal alkenes) attracted much attention and
emerged as powerful tools for the selective synthesis of olefins,
but those reactions required noble metal catalysts and
preparation of starting material olefins.3
naphthylmethyl pivalate and phenylacetonitrile.a
Scheme 1 Ni-catalyzed synthesis of (E)-olefins from benzylic alcohol
derivatives and arylacetonitriles via C-O activation.
aConditions: a mixture of 1a (0.1 mmol), 2a (0.15 mmol), Ni(COD)2, a
Another efficient method to access olefins is the
semihydrogenation of alkynes. However, the transformation
usually suffered from over-reduction and chemo-control.4
phosphine ligand (P/Ni = 2:1) and a base in the solvent (1.5 mL) was stirred
b
at the temperature indicated for 24 h, E/Z > 99:1. GC yield using tridecane
as an internal standard. cIn the absence of Ni catalyst.
a.State Key Laboratory of Chemo/Biosensing and Chemometrics, College of
Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China.
E-mail: chentieqiao@hnu.edu.cn
easily
available
benzylic
alcohol
derivatives
and
arylacetonitriles via C-O activation.5,6 This transformation
features high stereoselectivity and is applicable to prepare
various (E)-olefins including those functional molecules
(Scheme 1).1a,7
b.National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba,
Ibaraki 305-8565, Japan. E-mail: libiao-han@aist.go.jp
Electronic Supplementary Information (ESI) available: General information,
experimental procedures, copies of 1H and 13C NMR spectra for products. See DOI:
10.1039/b000000x/
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During the extensive studies on the cross coupling of C-O was employed under similar reaction conditions (Table 1, entry 9).
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electrophiles with Z-H compounds,8 we accidently found that 36% However, further increasing the amount ofDbOasI:e10d.i1d0n3’9t/Cim5CprCo1v0e00t5hDe
yield of 2-styrylnaphthalene 3a with high (E)-selectivity was reaction efficiency (Table 1, entry 10). t-BuONa and t-BuOLi acted as
produced when naphthylmethyl pivalate 1a was allowed to react effective base despite with relatively low yields (Table 1, entries 11
o
with phenylacetonitrile 2a in dioxane at 100 C in the presence of 5 and 12). This reaction occurred well with 5 mol% nickel complex,
mol% Ni(COD)2/dcype (1,2-bis(dicyclohexylphosphanyl)ethane) and either increasing or decreasing the loading lead to the decrease of
2 equiv t-BuOK (Table 1, entry 1). The interesting result drove us to
yield (Table 1, entries 13 and 14). At an elevating temperature, the
reaction also took place to give 3a in 86% yield. However, upon
lowering the temperature to 80 C, only 21% yield of 3a was given
Table 2 Ni-catalyzed synthesis of (E)-olefins from arylacetonitriles with
o
naphthyl-based derivativesa
(Table 1, entries 15 and 16). As to the solvent, this reaction also
proceeded readily in THF, but poorly in toluene and DMF (Table 1,
entries 17-19). In the absence of the Ni catalyst, a trace amount of
product was detected (Table 1, entry 20).
Table 3 Ni-catalyzed synthesis of (E)-olefins from arylacetonitriles with
benzylic alcohol derivatives.a
aConditions: 1 (0.1 mmol), 2 (0.3 mmol), Ni(COD)2 ( 10 mol%), dcype (10
a
Conditions: 1 (0.1 mmol), 2 (0.15 mmol), Ni(COD)2 (5 mol%), dppp (5
o
mol%), t-BuOK (3.0 equiv), dioxane (1.5 mL), 140 C, 24 h. Isolated yield..b
mol%), t-BuOK (0.25 mmol), dioxane (1.5 mL), 100 oC , 24 h. Unless
otherwise noted, R2 = C(O)Bu-t. Isolated yield. .bNi(COD)2 (10 mol%), dcype
(10 mol%), 150 oC, 24 h.
Ni(COD)2 ( 20 mol%), dcype (20 mol%).
This transformation is applicable to other substrates,
producing the corresponding (E)-olefins in good to high yields.
Thus, the carbamate reacted with phenylacetonitrile smoothly
to afford the corresponding product 3a in good yield under the
standard reaction conditions. Phenylacetonitriles with electron-
donating groups such as methyl, methoxy, amine and phenyl on
further investigate the transformation. Other phosphine ligands
selected were also effective for production of 3a with dppp (1,3-
bis(diphenylphosphanyl)propane) being the best choice (Table 1,
entries 2-8). 86% yield of 3a was produced when 2.5 equiv t-BuOK
2 | J. Name., 2012, 00, 1-3
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benzene ring coupled with naphthylmethyl pivalate 1a readily, dimethoxybenzyl pivalate coupled readily ViwewitAhrticle O2n-(li4ne-
DOI: 10.1039/C5CC10005D
yielding the expected (E)-olefins in moderate to excellent yields. methoxyphenyl)acetonitrile to produce the corresponding (E)-
The fluoro group survived in the current catalytic system. olefin 3x in 92% yield, which could be converted easily to the
However, when phenylacetonitriles with electron-withdrawing natural product resveratrol following the established
group like CF3 was employed as the substrate, only a trace procedures (Scheme 2, A).9 1,4-Bis((E)-2-methylstyryl)benzene
amount of product was detectable. 1-Naphthylacetonitrile also 3y is usually used as scintillator in Scintillation Counter and
was proved to be good substrate for the reaction, and the scintillation spectrometer. The functional molecule was easily
expected product 3j was generated in 76% yield. Worth noting is produced in 62% isolated yield via diolefination of 1,4-
that trisubstituted alkenes 3m and 3n were also prepared from phenylenedimethanol pivalates with 2-(o-tolyl)acetonitrile
the expected secondary arylacetonitriles or secondary benzylic under the present reaction conditions (Scheme 2, B).10 The
alcohol pivalates, albeit with only moderate E/Z selectivity. pharmaceutical adapalene could also be converted to the
However, when an aliphatic nitrile like acetonitrile was corresponding olefin 3z by reacting with phenylacetonitrile in
subjected into the reaction, no product was detected by GC-MS.
the current catalytic system after reduction and esterification
By switching the phosphine ligand dppp to dcype, the simpler (Scheme 2, C).
benzyl esters were also applicable to this reaction. As shown in
Table 3, benzyl pivalates coupled smoothly with various
phenylacetonitriles, producing the corresponding (E)-olefins in
good yields. Other pivalate derivatives bearing functional groups
on the benzene ring such as Me, t-Bu, OPh and SMe served well
in this transformation, furnishing the coupling products in good
to high yields (3p, 3s-3u). Notably, the heterocyclic 2-(pyridin-2-
yl) acetonitrile was proved to be good substrate and the
expected (E)-olefin 3v was produced in 61% yield with 99/1 (E)-
stereoselectivity. Benzyl pivalate also reacted with secondary
Scheme 3 Control experiments.
During the reaction of naphthylmethyl pivalate 1a with
phenylacetonitrile 2a, α-alkylated nitriles 4a generated from α-
alkylation via C-O activation was detected by GC-MS. We deduce
the α-alkylated nitriles would be the efficient reaction
intermediate. This is indeed. The resulting 4a could undergo
elimination, producing (E)-olefin 3a in high yield in the presence
of 1 equiv t-BuOK. Under the standard reaction conditions, (Z)-
stilbene remained intact and no trace amount of (E)-stilbene
was detectable (Scheme 3). Those results indicated that the
elimination would be a stereoselective E2 process.
benzyl cyanide smoothly, affording the desired product 3w in 64%
yield.
Scheme 4 Proposed mechanism. Ligands are omitted for clarity.
On the basis of the results described above and
literatures,11,12 a plausible mechanism is proposed as shown in
Scheme 4. Complex B generated from the oxidative addition of
Scheme 2 Synthesis of functional molecules.
The synthetic value of the transformation was further
displayed by the efficient synthesis of functional molecules.
Thus, by employing the nickel catalyzed reaction, 3,5-
Ni(0) complex
A with C-O electrophiles underwent ligand
exchange with a nitrile by the aid of a base, producing species C,
followed by reductive elimination to yield the α-alkylated
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Harris, L. E. Hanna, M. A. Greene, C. E. Moore and E. R. Jarvo,
nitriles 4 and regenerate Ni(0) complex A. Stereoselective E2
View Article Online
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R. Martin, J. Am. Chem. Soc., 201D4O, I:11306.1,03190/C652C; C(1n0)00M5D.
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elimination of the α-alkylated nitriles
corresponding (E)-olefins.
4
produces the
In summary, we have disclosed an efficient Ni-catalyzed
tandem reaction between arylacetonitriles and benzylic alcohol
derivatives. This transformation coupled α-alkylation of nitriles
with C-O electrophiles via C-O activation and subsequent E2
elimination, providing a simple and efficient method to access
various (E)-olefins with high stereoselectivity from the relatively
readily available starting materials.
Partial financial supports from NFSC (21403062, 21373080),
HNNSF 2015JJ3039 and the Fundamental Research Funds for the
Central Universities (Hunan University) are gratefully
acknowledged.
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10 Scintillator 3y is used to be prepared from reaction of 1-
(halomethyl)-2-methylbenzene with terephthalaldehyde via
Wittig process, which is under protection by patent, see: V. K.
Koul and B. R. Hirani, Indian 2006MU01558, patent, Sep. 19
2008.
11 K. Muto, J. Yamaguchi, A. Lei and K. Itami, J. Am. Chem. Soc.,
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