Aromatic-amide-derived olefins as a springboard: Isomerization-initiated palladium-catalyzed hydrogenation of olefins and reductive decarbonylation of acyl chlorides with hydrosilane

Article abstract of DOI:10.1002/chem.201200039

A highly efficient catalytic protocol for the isomerization of substituted amide-derived olefins is presented that successfully uses a hydride palladium catalyst system generated from [PdCl₂(PPh₃)₂] and HSi(OEt)₃. The Z to E isomerization was carried out smoothly and resulted in geometrically pure substituted olefins. Apart from the cis-trans isomerization of double bonds, the selective reduction of terminal olefins and activated alkenes was performed with excellent functional group tolerance in the presence of an amide-derived olefin ligand, and the products were obtained in high isolated yields (up to >99 %). Furthermore, the palladium/hydrosilane system was able to promote the reductive decarbonylation of benzoyl chloride when a (Z)-olefin with an aromatic amide moiety was used as a ligand. Copyright

Full text of DOI:10.1002/chem.201200039

DOI: 10.1002/chem.201200039
Aromatic-Amide-Derived Olefins as a Springboard: Isomerization-Initiated
Palladium-Catalyzed Hydrogenation of Olefins and Reductive
Decarbonylation of Acyl Chlorides with Hydrosilane
Xing-Feng Bai, Li-Wen Xu,* Long-Sheng Zheng, Jian-Xiong Jiang, Guo-Qiao Lai, and
Jun-Yan Shang[a]
Abstract: A highly efficient catalytic
protocol for the isomerization of sub-
stituted amide-derived olefins is pre-
sented that successfully uses a hydride
palladium catalyst system generated
from the cis–trans isomerization of
double bonds, the selective reduction
of terminal olefins and activated al-
kenes was performed with excellent
functional group tolerance in the pres-
ence of an amide-derived olefin ligand,
and the products were obtained in high
isolated yields (up to >99%). Further-
more,
the
palladium/hydrosilane
from [PdCl
(PPh3)2] and HSi
E
system was able to promote the reduc-
tive decarbonylation of benzoyl chlo-
ride when a (Z)-olefin with an aromat-
ic amide moiety was used as a ligand.
Keywords: alkenes · decarbonyla-
tion · isomerization · palladium ·
reduction
The Z to E isomerization was carried
out smoothly and resulted in geometri-
cally pure substituted olefins. Apart
Introduction
and selective construction of carbon–carbon double bonds,
there is a continuous demand to develop synthetic methods
for the synthesis of task-specific functional olefins. In addi-
tion, the functionalization and transformation of olefins is
an everlasting, synthetically important problem in organic
synthesis. Specifically, in the field of the application of func-
tional olefins in homogeneous catalysis, the significance of
substituted olefins in transition-metal-based catalysis is re-
flected in the potential application of such olefin-containing
compounds as ligands.[10,11]
Very recently, we have reported the preparation of amide-
derived substituted olefins by an unprecedented lateral se-
quential lithiation/silylation/Peterson condensation of terti-
ary aromatic amides (1), which provides an efficient method
to build-up functional olefins that could be used as a ligand
in palladium catalysis in good yields (Scheme 1).[12] How-
Highly efficient regio- and chemoselective synthesis of sub-
stituted olefins containing different carbon-linked functional
groups is still a challenge of particular importance in organic
synthesis.[1] Functional alkenes represent key and basic
structural features in organic compounds and are arguably
the most important and basic building blocks in organic
transformations. Preparative methods for the construction of
carbon–carbon double bonds have provided useful platforms
from which challenging complex targets and synthetic goals
can be reached.[2] Especially in recent years, significant ach-
ievements have been made in the synthesis of substituted
olefins through various protocols, such as the Wittig reac-
tion,[3] the Bamford–Stevens–Shapiro olefination,[4] the
Corey–Winter olefination,[5] the Julia–Lythgoe olefination,[6]
the Peterson olefination,[7] the Takai reaction,[8] or by alkene
metathesis.[9] Unavoidably, in these studies, the olefinations
still resulted in mixtures of cis- and trans-alkenes. It would
therefore be very useful to develop a reliable, mild, and
facile method for the conversion of alkene mixtures to geo-
metrically pure substituted olefins through isomerization.
Although much attention has been focused on the versatile
Scheme 1. The synthesis of amide-derived olefins; TMEDA=
tetramethylACTHNUTRGNEeNUG thylenediamine.
[a] X.-F. Bai, Prof. Dr. L.-W. Xu, L.-S. Zheng, Dr. J.-X. Jiang,
Prof. G.-Q. Lai, J.-Y. Shang
Key Laboratory of Organosilicon Chemistry and
Material Technology of Ministry of Education
Hangzhou Normal University, Hangzhou 310012 (P.R. China)
Fax : (+86)571-28865135
ever, similar to previous reports on olefination, mixtures of
cis- and trans-alkenes were formed unavoidably in most
cases. Although recent advances have been made using the
transition-metal-catalyzed isomerization of olefins or based
on photochemistry,[13] it was found that amide-derived ole-
fins containing bulky groups were very stable under many
E-mail: liwenxu@hznu.edu.cn
licpxulw@yahoo.com
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201200039.
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FULL PAPER
previously reported E/Z inter-
conversion
conditions.[12,13]
Therefore, the development of
a novel protocol of isomeriza-
tion for the preparation of sub-
stituted olefins as
a
single
isomer is highly desired.
Herein, we report on the devel-
opment of a new method of iso-
merization that is promoted by
palladium in the presence of
Scheme 2.
hydrosilanes. Furthermore, inspired by the palladium-cata-
lyzed isomerization of olefins with hydrosilanes, the influ-
ence of the amide-derived olefin on the palladium-catalyzed
hydrogenation of olefins and reductive decarbonylation of
acyl chlorides was studied in this manuscript. Instead of di-
hydrogen gas, we found that functional olefins with tertiary
aromatic amides could act as a highly efficient initiator or
promoter in the palladium-catalyzed reduction of activated
olefins and terminal non-substituted olefins with hydrosi-
lanes. In addition, in a further study, we found the aromatic
amide-derived olefin also exhibited dramatic ligand effects
on the reductive decarbonylation of aromatic acyl chlorides
to the corresponding aromatics.
isomer 3a in the presence of triethoxysilane (HSi
Scheme 2). Control experiments proved that the palladium
source, the phosphine, or the HSi(OEt)3 individually or in
a combination of two could not catalyze the isomerization.
Interestingly, the type of palladium source is also crucial to
ACHTUNGTRENNUNG(OEt)3;
AHCTUNGTRENNUNG
the cis–trans double-bond isomerization because Pd
resulted in complete hydrogenation of 2a in the presence of
excess HSi(OEt)3 (Scheme 2, >99% yield). It was also
shown that other transition metal catalysts, such as [RhCl-
(PPh3)] and RuCl3, were not able to catalyze the isomeriza-
ACHTUNGTRENNUNG(OAc)2
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
tion fully to give the geometrically pure (E)-isomer (see the
Supporting Information). On the basis of these promising
findings, we considered that the reaction conditions, [PdCl2-
ACHUNTGRENN(UG PPh3)2], and HSiACHTUGNTERN(NUGN OEt)3, could be exploited for the isomeri-
zation of (Z)-1,2-diphenylethene. The result confirmed that
the in situ generated palladium hydride complex was an effi-
cient catalyst for the isomerization of the carbon–carbon
double bond of (Z)-1,2-diphenylethene, and only (E)-1,2-di-
phenylethene was detected (Scheme 3).
Results and Discussion
Isomerization of aromatic-amide-derived olefins: Previous
studies have demonstrated that palladium can promote the
isomerization of cis-alkenes to give trans-alkenes.[14] In par-
ticular, it was found that palladium hydrides were efficient
catalysts in the isomerization of double bonds conjugated to
aromatic systems in the presence of hydrogen (H2) or tribu-
tyltin hydride (Bu3SnH). Very recently, Lindhardt and
Skrydstrup[14j] reported the application of an in situ generat-
ed bulky palladium(II) hydride catalyst derived from a mix-
ture of PdACHTUNGTRENNUNG(dba)2, PACHTUNGTRENNUNG(tBu)3, and isobutyryl chloride in the cis–
Scheme 3.
trans isomerization of double bonds. However, the draw-
backs of previous protocols are unavoidable, such as highly
toxic reagents, high pressure conditions, and expensive palla-
dium complexes, or use of an air-sensitive phosphane ligand;
therefore, it is highly desirable to develop a novel and effi-
cient approach to provide an effective palladium catalyst for
isomerization that is also beneficial for the chemistry of pal-
ladium.
With the optimized conditions in hand, we decide to in-
vestigate the reactivity of the palladium catalyst system on
different (Z/E)-isomer mixtures of olefins with tertiary aro-
matic amides. In all cases in Scheme 4, applying a 1 mol%
palladium catalyst loading promoted the quantitative iso-
merization of (Z/E)-isomer mixtures of 2 in the presence of
Initially, to obtain the geometrically pure isomer of the
functional olefins with tertiary aromatic amides (2), we
found it was difficult to provide the geometrically pure (Z)-
or (E)-isomer completely under the palladium-catalyzed iso-
merization conditions reported previously. Inspired by previ-
ous findings, we hypothesized that hydrosilane could be
used as a hydride source for the in situ formation of a highly
efficient palladium hydride catalyst for the isomerization of
double bonds. The screening of transition-metal catalysts re-
1.0 equivalent of HSiACTHNGUTERN(NUG OEt)3. Only the (E)-isomer was ob-
tained under the reaction conditions (Scheme 4). Thus, the
isomerization makes the amide-derived olefins (3) useful in
organic synthesis due to the geometrically pure conforma-
tion.
An isomerization mechanism of the palladium-catalyzed
cis–trans conversion of double bonds under a H2 atmosphere
has been reported previously.[14] This mechanism involves
the formation of palladium hydride complexes by a repeated
olefin addition and b-hydride elimination. In our proposed
mechanism of palladium-catalyzed isomerization of amide-
vealed that [PdCl
2ACHTUNGTRENNUNG(PPh3)2] could afford full isomerization of
(Z/E)-isomer mixtures of 2a to the corresponding (E)-
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L.-W. Xu et al.
tivated olefins, which would be beneficial to the understand-
ing of ligand effects of amide-derived olefins in the isomeri-
zation. A previous report indicated that the amide-derived
olefin proved to be an effective ligand in the palladium-cata-
lyzed Suzuki cross-coupling reaction.[12] All of this informa-
tion and our hypothesis prompted us to extend the study of
isomerization to selective hydrogenation. With HSiACHTNUTRGNEUNG(OEt)3 as
the reductant, palladium-catalyzed hydrogenation of styrene
was not an easy transformation due to side hydrosilylation.
We found that the ratio of selective hydrogenation to hydro-
silylation was low (48:15 of yield) in the presence of Pd-
AHCTUNGTRENNUNG
CTHUNGTRENNUNG
although the yield was moderate (48%). Although palladi-
um-based catalysts are known to catalyze hydrosilylation re-
actions and coupling reactions, to our surprise, these side re-
actions were not observed in the presence of amide-derived
olefin (Z)-3a. To obtain an improved conversion, we expect-
ed that the amide-derived olefin (Z)-3a could be used as
a ligand on the basis of the illustration of palladium-cata-
lyzed isomerization. As expected, under the same reaction
conditions, 1-ethylbenzene was obtained quantitatively and
no hydrosilylated product, triethoxyphenylethylsilane, was
detected (Scheme 6). Note, that free triphenylphosphine was
Scheme 4. Palladium-catalyzed isomerization of amide-derived olefins.
derived olefins 2, an equilibrium between a palladium(dihy-
drido)–substrate complex and palladium hydride complexes
was possible, followed by hydride addition to the olefin and
b-hydride elimination to complete the cis–trans isomeriza-
tion (Scheme 5).
Scheme 6. The effect of the amide-derived olefin in the palladium-cata-
lyzed hydrogenation of styrene.
confirmed in solution, which supported the existence of an
equilibrium between the palladium(dihydrido)olefin com-
plex and the palladium(dihydrido) triphenylphosphine com-
plex. Similar to a previous report,[12] the (Z/E) isomer mix-
ture of 2a and (E)-3a exhibited poorer activity than that of
the corresponding (Z)-isomer. From these findings, it was
concluded that the palladium(dihydrido)olefin complex in
situ generated from (Z)-3a exhibited excellent activity in
hydride transfer, thus resulted in the complete hydrogena-
tion of styrene. Notably, when the amide-derived olefin
ligand (Z)-3a was analyzed after the reaction, only (E)-3a
was observed, with no trace of hydrogenated product.
Scheme 5. The mechanistic process of palladium/HSiACTHNUGTRENUNG(OEt)3-promoted
cis–trans isomerization of double bonds.
With the optimized conditions established in the palladi-
um-catalyzed reduction of styrene in the presence of hydro-
silane and to further investigate the utility of amide-derived
olefin (Z)-3a in the palladium catalyzed hydrogenation of
olefins, reduction reactions of activated alkenes and termi-
nal olefins were examined. As shown in Scheme 7, the re-
duction of these substrates was performed in THF with
Aromatic-amide-derived olefin-assisted palladium-catalyzed
reduction of olefins: To elucidate the role of amide-derived
olefins (2) in organic synthesis based on the mechanistic
process of the palladium-catalyzed isomerization, we hy-
pothesized that the palladium(dihydrido)olefin (2) complex
(I or II) could be a highly efficient in situ generated palladi-
um intermediate for hydrogenation of terminal olefins or ac-
[PdCl
2ACHTUTGNRENNUG(PPh3)2], HSiACHTUNGTERN(NUGN OEt)3, and aromatic-amide-derived
olefin (2a or 3a). In most cases, complete conversion to the
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Aromatic-Amide-Derived Olefins
FULL PAPER
process for, for example, removal of traceless linkers and
unwanted functional groups. Similar to the above findings,
in the reductive decarbonylation reaction, the olefin ligand
(Z)-3a was transformed to (E)-3a in the last step. It appears
that because the palladium(dihydrido)olefin complex de-
rived from (Z)-3a easily adds to benzoyl chloride, then the
predominant reaction is palladium-catalyzed decarbonyla-
tion. Although the mechanism of the (Z)-3a-promoted pal-
ladium-catalyzed hydrogenation of olefins and reductive de-
carbonylation of acyl chloride has not yet been confirmed
accurately, we assumed that the reaction proceeded through
the process illustrated in Scheme 9 on the basis of experi-
Scheme 7. Palladium-catalyzed hydrogenation of olefins promoted by
amide-derived olefin (Z)-3a.
corresponding reduction product was achieved under mild
conditions. For example, the reaction of terminal olefins, cy-
clohexenone, and maleimide-derived alkenes, led to excel-
lent isolated yields. No further purification was necessary to
afford pure material. Although aromatic enones underwent
complete conversion, trace hydrosilylated product was de-
tected so that the isolated yields of corresponding products
were only in the range of 75 to 82%.
Aromatic-amide-derived olefin-assisted palladium-catalyzed
reductive decarbonylation of acyl chlorides: To gain more
insight into the palladium(II) hydride catalysis, the effect of
the amide-derived olefin ligand was examined in the selec-
tive reduction of benzoyl chloride under identical reaction
conditions. As shown in Scheme 8, reductive decarbonyla-
Scheme 9. The mechanistic process of the amide-derived olefin (Z)-3a-
promoted palladium-catalyzed hydrogenation of olefins and reductive de-
carbonylation of acyl chlorides.
mental results. In the catalytic cycle, the amide-derive olefin
(Z)-3a acted as a highly efficient ligand and substrate suc-
cessively, which means that the amide-derived olefin used in
these palladium-catalyzed reduction reactions is not only
a simple olefin ligand but also a springboard to activated
palladium catalysts.
Conclusion
A highly efficient catalytic protocol for the isomerization of
substituted amide-derived olefins was presented using a hy-
dride palladium catalyst system generated from [PdCl2-
ACHUNTGRENN(UG PPh3)2] and HSiACHTUNTGNER(NUGN OEt)3. The Z to E isomerization was car-
Scheme 8. Palladium-catalyzed reductive decarbonylation promoted by
ried out smoothly and resulted in geometrically pure substi-
tuted olefins. The hydrosilane-promoted palladium-cata-
lyzed isomerization could also be applied to the isomeriza-
tion of diphenylethene. Apart from the cis–trans
isomerization of double bonds, with the aid of the amide-de-
rived olefin ligand, the selective reduction was performed
with excellent functional group tolerance and the products
the amide-derived olefin (Z)-3a.
tion occurred in the presence of olefin ligand (Z)-3a, where-
as the reaction was sluggish with trace conversion and the
starting material remained in the absence of olefin ligand or
in the presence of (E)-3a. This may prove to be a useful
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L.-W. Xu et al.
A. C. Burns, T. R. Hoye, Org. Lett. 2011, 13, 703–705; g) R. Kumar,
P. Pradhan, B. Zajc, Chem. Commun. 2011, 47, 3891–3893.
were produced in high isolated yields. Furthermore, the pal-
ladium/hydrosilane system was able to promote the reduc-
tive decarbonylation of benzoyl chloride in the presence of
the amide-derived olefin. Although the mechanism via a pal-
ladium(dihydrido)olefin complex needs to be supported by
direct evidence, reaction results revealed that the in situ
generated hydride palladium complex was a key catalyst in
the presence of the amide-derived olefin. In other words,
the amide-derived olefin used as a special olefin ligand di-
rected palladium-catalyzed selective hydrogenation of acti-
vated olefins or terminal olefins and the reductive decarbon-
ylation of acyl chlorides in the presence of hydrosilanes suc-
cessfully. Finally, based on the above findings and the possi-
ble mechanistic process, we have established a novel concept
of relay palladium catalysis, that is, the palladium-catalyzed
isomerization of an olefin ligand to initiate/activate a palladi-
um-catalyzed organic transformation. Additional investiga-
tions are ongoing to obtain more reaction performances and
more transformations with regard to the amide-derived
olefin with a chiral auxiliary used as a chiral ligand in transi-
tion-metal catalysis.
[7] a) D. J. Peterson, J. Org. Chem. 1968, 33, 780–784; b) D. J. Ager,
Org. React. 1990, 38, 1–223; c) N. Assadi, S. Pogodin, I. Agranat,
Eur. J. Org. Chem. 2011, 6773–6780; d) G. Q. Wei, T. Cohen, Synlett
2011, 2697–2700; e) J. McNulty, P. Das, D. Gosciniak, Tetrahedron
Lett. 2008, 49, 281–285; f) M. C. Fernꢂndez, A. Diaz, J. J. Guillin, O.
Blanco, M. Ruiz, V. Ojea, J. Org. Chem. 2006, 71, 6958–6974;
g) F. J. Pulido, A. Barberdo, Nat. Protoc. 2006, 1, 2068–2074.
[8] K. Takai, K. Nitta, K. Utimoto, J. Am. Chem. Soc. 1986, 108, 7408–
7410.
[9] a) R. H. Grubbs, Tetrahedron 2004, 60, 7117–7140; b) T. Paul, R. B.
Andrade, Tetrahedron Lett. 2007, 48, 5367–5370; c) R. P. Murelli,
M. L. Snapper, Org. Lett. 2007, 9, 1749–1752; d) S. Alam, H. Dhi-
mane, Synlett 2010, 2923–2927. A. G. Wenzel, G. Blake, D. G. Van-
derVelde, R. H. Grubbs, J. Am. Chem. Soc. 2011, 133, 6429–6439.
[10] Recent reviews: a) F. Glorius, Angew. Chem. 2004, 116, 3444–3446;
Angew. Chem. Int. Ed. 2004, 43, 3364–3366; b) J. B. Johnson, T.
Rovis, Angew. Chem. 2008, 120, 852–884; Angew. Chem. Int. Ed.
2008, 47, 840–871; c) C. Defieber, H. Grꢃtzmacher, E. M. Carreira,
Angew. Chem. 2008, 120, 4558–4579; Angew. Chem. Int. Ed. 2008,
47, 4482–4502; d) R. Shintani, T. Hayashi, Aldrichimica Acta 2009,
42, 31–38 and references cited therein.
[11] Recent examples: a) G. Mora, S. van Zutphen, C. Thoumazet, X. F.
Le Goff, L. Richard, H. Grutzmacher, P. Le Floch, Organometallics
2006, 25, 5528–5532; b) Z. Q. Wang, C. G. Feng, M. H. Xu, G. Q.
Lin, J. Am. Chem. Soc. 2007, 129, 5336–5337; c) A. Kempter, C.
Gemel, R. A. Fischer, Chem. Eur. J. 2007, 13, 2990–3000; d) R.
Shintani, Y. Sannohe, T. Tsuji, T. Hayashi, Angew. Chem. 2007, 119,
7415–7418; Angew. Chem. Int. Ed. 2007, 46, 7277–7280; e) R. Shin-
tani, S. Park, T. Hayashi, J. Am. Chem. Soc. 2007, 129, 14866–14867;
f) T. Gendrineau, O. Chuzel, H. Eijsberg, J. P. Genet, S. Darses,
Angew. Chem. 2008, 120, 7783–7786; Angew. Chem. Int. Ed. 2008,
47, 7669–7672; g) W. Shi, Y. Luo, X. Luo, L. Chao, H. Zhang, J.
Wang, A. Lei, J. Am. Chem. Soc. 2008, 130, 14713–14720; h) H.
Zhang, X. Luo, K. Wongkhan, H. Duan, Q. Li, L. Zhu, J. Wang,
A. S. Batsanov, J. A. K. Howard, T. B. Marder, A. Lei, Chem. Eur. J.
2009, 15, 3823–3829; i) T. Minuth, M. M. K. Boysen, Org. Lett. 2009,
11, 4212–4215; j) I. Nakamura, C. S. Chan, T. Araki, M. Terada, Y.
Yamamoto, Adv. Synth. Catal. 2009, 351, 1089–1100; k) M. L. Buil,
R. Castarlenas, M. A. Esteruelas, S. Izquierdo, R. Lalrempuia, E.
Onate, Organometallics 2010, 29, 876–882; m) C. Martꢄn, J. M.
Munoz-Molina, A. Locati, E. Alvarez, F. Maseras, T. R. Blederrain,
P. J. Perez, Organometallics 2010, 29, 3481–3489; n) R. Shintani, S.
Isobe, M. Takeda, T. Hayashi, Angew. Chem. 2010, 122, 3883–3886;
Angew. Chem. Int. Ed. 2010, 49, 3795–3798; o) T. Nishimura, Y.
Maeda, T. Hayashi, Angew. Chem. 2010, 122, 7482–7485; Angew.
Chem. Int. Ed. 2010, 49, 7324–7327; p) S. S. Zhang, Z. Q. Wang,
M. H. Xu, G. Q. Lin, Org. Lett. 2010, 12, 5546–5549; q) G. Chen, J.
Gui, L. Li, J. Liao, Angew. Chem. 2011, 123, 7823–7827; Angew.
Chem. Int. Ed. 2011, 50, 7681–7685; r) T. J. Hoffman, E. M. Car-
reira, Angew. Chem. 2011, 123, 10858–10862; Angew. Chem. Int.
Ed. 2011, 50, 10670–10674; s) W. W. Wei, J. Y. Yeh, T. S. Kuo, H. L.
Wu, Chem. Eur. J. 2011, 17, 11405–11409; t) C. Shao, H. J. Yu, N. Y.
Wu, P. Tian, R. Wang, C. G. Feng, G. Q. Lin, Org. Lett. 2011, 13,
788–791; u) Q. Li, Z. Dong, Z. X. Yu, Org. Lett. 2011, 13, 1122–
1125; v) R. Shintani, M. Takeda, Y. T. Soh, T. Ito, T. Hayashi, Org.
Lett. 2011, 13, 2977–2979; w) W. Y. Qi, T. S. Zhu, M. H. Xu, Org.
Lett. 2011, 13, 3410–3413; x) Y. Wang, X. Feng, H. Du, Org. Lett.
2011, 13, 4954–4957.
Acknowledgements
Financial support by the National Natural Science Foundation of China
(NSFC, No. 20973051 and 21173064), the Program for Excellent Young
Teachers in Hangzhou Normal University (HNUEYT, JTAS 2011-01-
014), and the Most Important Subjects of Organic Chemistry of Zhejiang
Province is appreciated.
[1] Selected reviews: a) C. Dugave, L. Demange, Chem. Rev. 2003, 103,
2475–2532; b) R. Uma, C. Crꢁvisy, R. Grꢁe, Chem. Rev. 2003, 103,
´
27–52; c) N. Kuznik, S. Krompiec, Coord. Chem. Rev. 2007, 251,
222–233; selected recent examples: d) T. C. Lin, Q. Zheng, C. Y.
Chen, G. S. He, W. J. Huang, A. I. Ryasnyanskiy, P. N. Prasad,
Chem. Commun. 2008, 389–391; e) Y. L. Shi, S. M. Peterson, W. W.
Haberaecker, S. A. Blum, J. Am. Chem. Soc. 2008, 130, 2168–2169;
f) C. L. Sun, Y. Wang, X. A. Zhou, Z. H. Wu, B. J. Li, B. T. Guan,
Z. J. Shi, Chem. Eur. J. 2010, 16, 5844–5847; g) L. Ilies, S. Asako, E.
Nakamura, J. Am. Chem. Soc. 2011, 133, 7672–7675.
[2] S. E. Kelly, in Comprehensive Organic Synthesis, Vol. 1 (Eds.: B. M.
Trost, I. Fleming), Pergamon, Oxford, 1991, pp. 729–818.
[3] a) J. Boutagy, R. Thomas, Chem. Rev. 1974, 74, 87–99; b) B. E. Mar-
yanoff, A. B. Reitz, Chem. Rev. 1989, 89, 863–927; c) D. J. Phillips,
K. S. Pillinger, W. Li, A. E. Taylor, A. E. Graham, Chem. Commun.
2006, 2280–2282; d) G. A. Molander, R. Figueroa, J. Org. Chem.
2006, 71, 6135–6140; e) F. Alonso, P. Riente, M. Yus, Eur. J. Org.
Chem. 2009, 6034–6042; f) E. Ramirez, M. Sanchez, R. L. Meza-
Leon, L. Quintero, F. Sartillo-Piscil, Tetrahedron Lett. 2010, 51,
2178–2180; g) D. J. Dong, H. H. Li, S. K. Tian, J. Am. Chem. Soc.
2010, 132, 5018–5020; h) R. Zhou, C. Z. Wang, H. B. Song, Z. J. He,
Org. Lett. 2010, 12, 976–979.
[12] L. W. Xu, X. H. Chen, H. Shen, Y. Deng, J. X. Jiang, K. Jiang, G. Q.
Lai, C. Q. Sheng, Eur. J. Org. Chem. 2012, 290–298.
[4] R. M. Adlington, A. G. M. Barrett, Acc. Chem. Res. 1983, 16, 55–59.
[5] a) E. Block, Org. React. 1984, 30, 457–566; b) G. W. Wang, Z. H.
Huang, E. I. Negishi, Org. Lett. 2008, 10, 3223–3226.
[6] a) M. Julia, J. M. Paris, Tetrahedron Lett. 1973, 14, 4833–4836;
b) B. N. Manjunath, N. P. Sane, I. S. Aidhen, Eur. J. Org. Chem.
2006, 2851–2855; c) M. E. Lebrun, P. Le Marquand, C. Berthelette,
J. Org. Chem. 2006, 71, 2009–2013; d) L. G. Zhu, C. F. Ni, Y. C.
Zhao, J. B. Hu, Tetrahedron 2010, 66, 5089–5100; e) A. Senthilmuru-
gan, I. S. Aidhen, Eur. J. Org. Chem. 2010, 555–564; f) E. C. Izgu,
[13] Selected examples: a) T. W. Gibson, P. Strassburger, J. Org. Chem.
1976, 41, 791–793; b) M. Kodomari, T. Sakamoto, S. Yoshitomi,
Bull. Chem. Soc. Jpn. 1989, 62, 4053; c) N. Iranpoor, E. Mottaghine-
jad, J. Organomet. Chem. 1992, 423, 399–404; d) M. A. Ali, Y.
Tsuada, Chem. Pharm. Bull. 1992, 40, 2842–2844; e) E. N. Jacobsen,
L. Deng, Y. Furukawa, L. E. Martinꢁz, Tetrahedron 1994, 50, 4323–
4334; f) R. E. Martin, J. Bartek, F. Diederich, R. R. Tykwinski, E. C.
8178
www.chemeurj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2012, 18, 8174 – 8179

Aromatic-Amide-Derived Olefins
FULL PAPER
Meister, A. Hilger, H. P. Hans, J. Chem. Soc. Perkin Trans. 2 1998,
233–242; g) T. Bosanac, J. Yang, C. S. Wilcox, Angew. Chem. 2001,
113, 1927–1931; Angew. Chem. Int. Ed. 2001, 40, 1875–1879;
h) M. M. Baag, A. Kar, N. P. Argade, Tetrahedron 2003, 59, 6489–
6492; i) M. Mirza-Aghayan, R. Boukherroub, M. Bolourtchain, M.
Hoseini, K. Tabar-Hydar, J. Organomet. Chem. 2003, 678, 1–4;
j) S. S. Hepperle, Q. Li, A. L. L. East, J. Phys. Chem. A 2005, 109,
10975–10981; k) M. A. Maryam, B. Rabah, B. Mohammad, Appl.
Organomet. Chem. 2006, 20, 214–219; l) H. J. Lim, C. R. Smith,
T. V. RajanBabu, J. Org. Chem. 2009, 74, 4565–4572; m) J. Fan, C.
Wan, Q. Wang, L. Gao, X. Zheng, Z. Wang, Org. Biomol. Chem.
2009, 7, 3168–3172; n) R. Shen, T. Chen, Y. Zhao, R. Qiu, Y. Zhou,
S. Yin, X. Wang, M. Goto, L. B. Han, J. Am. Chem. Soc. 2011, 133,
17037–17044.
Yu, M. Gaunt, J. B. Spencer, J. Org. Chem. 2002, 67, 4627–4629;
d) J. O. Dunne, S. B. Duckett, D. Konya, K. Q. LeÇero, E. Drent, J.
Am. Chem. Soc. 2004, 126, 16708–16709; e) A. M. Kluwer, T. S. Ko-
blenz, T. Jonischkeit, K. Woelk, C. Elesevier, J. Am. Chem. Soc.
2005, 127, 15470–15480; f) I. S. Kim, G. R. Dong, Y. H. Jung, J. Org.
Chem. 2007, 72, 5424–5426; g) B. Brandt, J. H. Fischer, W. Ludwig,
J. Libuda, F. Zaera, S. Schauermann, H. J. Freund, J. Phys. Chem. A
J. Phys. Chem. C. 2008, 112, 11408–11420; h) C. Luciano, S. Claudio,
V. Fabiano, Organometallics 2008, 27, 3577–3581; i) W. Ludwig, A.
Savara, S. Schauermann, Dalton Trans. 2010, 39, 8484–8491; j) D.
Gauthier, A. T. Lindhardt, E. P. K. Olsen, J. Overgaad, T. Skrydstr-
up, J. Am. Chem. Soc. 2010, 132, 7998–8009.
[14] a) P. Robert, R. Roman, J. Organomet. Chem. 1988, 341, 549–557;
b) J. Yu, J. B. Spencer, J. Am. Chem. Soc. 1997, 119, 5257–5258; c) J.
Received: January 5, 2012
Published online: May 22, 2012
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