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Nickel-Catalyzed Coupling of Carbonyl Compounds and Alkynes or 1 3-Dienes An Efficient Method for the Preparation of Allylic Homoallylic and Bishomoallylic Alcohols.

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Highlights
Ni-Catalyzed Coupling Reactions
Nickel-Catalyzed Coupling of Carbonyl Compounds and
Alkynes or 1,3-Dienes: An Efficient Method for the
Preparation of Allylic, Homoallylic, and Bishomoallylic
Alcohols
Shin-ichi Ikeda*
Keywords:
alcohols · C C coupling · catalysis · multicomponent
reactions · nickel
The alkenylation, allylation, and homoallylation of carbonyl compounds,
which gives allylic, homoallylic, and
bishomoallylic alcohols, respectively,
are important processes in the formation of carbon–carbon bonds. However,
in these approaches, the preparation of
the corresponding alkenylating, allylating, and homoallylating reagents, which
often requires troublesome procedures,
is unavoidable.[1–5] Recently, new nickelcatalyzed coupling reactions of a carbonyl compound (e.g., aldehyde or ketone) and an unsaturated substrate (e.g.,
alkyne or 1,3-diene) with an organometallic or metal hydride have been
reported, and these offer more efficient
methods to give the desired alcohols
without the in situ generation of alkenylating, allylating, and homoallylating
reagents.
Montgomery et al. developed the
nickel-catalyzed inter- and intramolecular three-component coupling of aldehydes and alkynes with organozinc reagents to produce tri- or tetrasubstituted
allylic alcohols with regio- and stereoselectivity.[6a,b] For the preparation of a
bicyclic nitrogen heterocycle, the catalytic system of [Ni(cod)2] and nBu3P is
highly effective for the Et3SiH-mediated
[*] Dr. S. Ikeda
Graduate School of Pharmaceutical
Sciences
Nagoya City University
Tanabe-dori, Mizuho-ku
Nagoya 467-8603 (Japan)
Fax: (+ 81) 52-836-3462
E-mail: ikeshin@phar.nagoya-cu.ac.jp
5120
reductive cyclization of alkynes (e.g., 1),
which possess a tethered aldehyde
group. This process leads to the construction of an alkaloid framework, such
as 2 (Scheme 1).[6c,d] The reaction proceeds via an oxanickelacycle intermediate 3, which is derived from the oxidative cyclization of a Ni0 complex with
the aldehyde and alkyne units of 1. The
oxanickelacycle 3 reacts with Et3SiH to
produce species 4, which then undergoes reductive elimination to give 2.
This method allows for direct introduction of the allylic alcohol unit, with the
completely stereoselective introduction
of an exocyclic carbon–carbon double
bond.
Jamison and co-workers developed
the intermolecular reductive coupling of
internal alkynes and aldehydes (which
was not possible with the Montgomery
method[6b]) by using Et3B as a reducing
agent.[7a] This reaction is performed in
the presence of [Ni(cod)2] and nBu3P in
THF or toluene, and gives trisubstituted
allylic alcohols via an oxanickelacycle.
The same group recently reported the
enantioselective reductive coupling of
aldehydes and alkynes using Et3B
(Scheme 2).[7b,c] When (+)-(neomenthyl)diphenylphosphane (NMDPP) is
treated as a chiral ligand in this catalytic
reaction, which was carried out in a
solvent composed of equal volumes of
EtOAc and 1,3-dimethyl-2-imidazolidinone (DMI), a trisubstituted allylic
alcohol is obtained in 96 % ee with high
regio- and stereoselectivity. The high
enantioselectivity provided by NMDPP
in the reaction can be explained by a
cooperative effect between the steric
properties of the ligand and the electronic differences of the alkyne substituents.
Mori et al. developed the nickelcatalyzed cyclization of 1,3-dienes 5,
which possess a tethered aldehyde group
(Scheme 3).[8] Treatment of 5 with
diisobutylaluminium
acetylacetonate
([iBu2Al(acac)]) in the presence of a
Scheme 1. Nickel-catalyzed reductive cyclization of aldehyde-functionalized alkyne 1 (L = nBu3P).
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/anie.200301673
Angew. Chem. Int. Ed. 2003, 42, 5120 –5122
Angewandte
Chemie
Scheme 2. Nickel-catalyzed enantioselective reductive coupling of an aldehyde and an alkyne
using Et3B (R = CH2NHBoc, L* = (+)-NMDPP).
Scheme 3. Nickel-catalyzed reductive cyclization of 5, a 1,3-diene with a tethered aldehyde
group, and [iBu2Al(acac)] or Et3SiH.
catalytic amount of [Ni(cod)2] and Ph3P
in THF at 0 8C yields 7, which has a
terminal alkene group.[8b] The reaction
proceeds via the transmetalation of an
oxanickelacycle intermediate 6, which is
derived from a Ni0 complex with the
aldehyde and diene units of 5 and
[iBu2Al(acac)]. Interestingly, when the
reaction was performed with Et3SiH
instead of [iBu2Al(acac)], compound 9
with an internal alkene group was obtained.[8b,c] In the cyclization, 5 reacts
with a nickel hydride complex, which is
formed by the oxidative addition of
Et3SiH to the Ni0 complex, to produce
a p-allyl nickel intermediate 8. Allylation of the p-allyl nickel moiety in 8 to
the tethered aldehyde yields 9. These
cyclizations complement each other to
afford 7 (via an oxanickelacycle–transmetalation process) or 9 (via a standard
allylation process) using the same catalytic system ([Ni(cod)2] and Ph3P) deAngew. Chem. Int. Ed. 2003, 42, 5120 –5122
pending on the different reducing reagents ([iBu2Al(acac)] or Et3SiH) that are
employed.
For the intermolecular reaction with 1,3-diene, Baker
and Crimmin reported the
nickel-catalyzed or -promoted coupling with aldehydes to
give homoallyl alcohols as a
mixture of 1:1, 2:1, and 3:1
adducts of the diene and
aldehyde, each of which consisted of many possible regioand stereoisomers.[9] Tamaru
et al. have since developed
the regio- and stereoselective
nickel-catalyzed coupling of
carbonyl compounds and 1,3dienes using organoboron or
organozinc reagents.[10] Thus,
isoprene is treated with aldehyde and Et3B in the preswww.angewandte.org
ence of [Ni(acac)2] in THF at room
temperature to provide the 1:1 adduct of
the diene and aldehyde exclusively
(Scheme 4).[10b] The reaction formally
corresponds to a reductive coupling of
the C1–C2 double bond of isoprene and
the carbonyl group of the aldehyde,
where Et3B acts as a reducing agent, to
give the bishomoallylic alcohol 10, and
not the homoallylic alcohol. Moreover,
the reaction exhibits high 1,3-asymmetric induction, to provide 1,3-anti-10 in
preference to 1,3-syn-10. The use of
Et2Zn instead of Et3B is particularly
effective for the reaction of saturated
aldehydes and ketones, where the latter
reagent is unsuccessful.[10c] In contrast,
coupling with Me2Zn or Me3B led to the
formation of homoallylic alcohols 11
(Scheme 5).[10d,e]
Carbon–carbon bond formation is a
fundamental process in synthetic organic chemistry. Therefore, multicomponent reactions, which permit complex
molecules to be reasonably well constructed in a single operation, are fascinating processes. The nickel-catalyzed
multicomponent couplings highlighted
here bring about the formal alkenylation,
allylation, and homoallylation of carbonyl compounds via the transmetalation of
an oxanickelacycle intermediate with
organometallic reagents. The analogous
nickelacycle derived from enones and
unsaturated substrates leads to a different multicomponent coupling.[6a, 11]
Scheme 4. Nickel-catalyzed reductive coupling of an aldehyde and
a 1,3-diene using Et3B or Et2Zn.
Scheme 5. Nickel-catalyzed coupling of an aldehyde and a 1,3-diene using Me3B or Me2Zn.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5121
Highlights
[1] a) H. Jin, J.-i. Uenishi, W. J. Christ, Y.
Kishi, J. Am. Chem. Soc. 1986, 108, 5644;
b) K. Takai, M. Tagashira, T. Kuroda, K.
Oshima, K. Utimoto, H. Nozaki, J. Am.
Chem. Soc. 1986, 108, 6064.
[2] a) W. Oppolzer, R. N. Radinov, Helv.
Chim. Acta 1992, 75, 170; b) W. Oppolzer, R. N. Radinov, J. Am. Chem. Soc.
1993, 115, 1593.
[3] a) P. Wipf, W. Xu, Tetrahedron Lett.
1994, 35, 5197; b) P. Wipf, S. Ribe, J.
Org. Chem. 1998, 63, 6454.
[4] Y. Yamamoto, A. Asao, Chem. Rev.
1993, 93, 2207.
[5] H. Yasuda, K. Tatsumi, A. Nakamura,
Acc. Chem. Res. 1985, 18, 120.
[6] a) J. Montgomery, Acc. Chem. Res. 2000,
33, 467; b) E. Oblinger, J. Montgomery,
J. Am. Chem. Soc. 1997, 119, 9065; c) X.Q. Tang, J. Montgomery, J. Am. Chem.
Soc. 1999, 121, 6098; d) X.-Q. Tang, J.
5122
Montgomery, J. Am. Chem. Soc. 2000,
122, 6950; e) For the preparation of
homoallylic alcohols by cyclization of
allenes with a tethered aldehyde: J.
Montgomery, M. Song, Org. Lett. 2002,
4, 4009.
[7] a) W.-S. Huang, J. Chan, T. F. Jamison,
Org. Lett. 2000, 2, 4221; b) E. A. Colby,
T. F. Jamison, J. Org. Chem. 2003, 68,
156; c) K. M. Miller, W.-S. Huang, T. F.
Jamison, J. Am. Chem. Soc. 2003, 125,
3442; d) S. J. Patel, T. F. Jamison, Angew. Chem. 2003, 115, 1402; Angew.
Chem. Int. Ed. 2003, 42, 1364.
[8] a) Y. Sato, M. Takimoto, M. Mori, J.
Synth. Org. Chem. Jpn. 2001, 59, 576,
and references therein; b) Y. Sato, M.
Takimoto, M. Mori, J. Am. Chem. Soc.
2000, 122, 1624; c) Y, Sato, M. Takimoto, K. Hayashi, T. Katsuhara, K.
Takagi, M. Mori, J. Am. Chem. Soc.
1994, 116, 9771.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
[9] R. Baker, M. J. Crimmin, J. Chem. Soc.
Perkin Trans. 1 1979, 1264.
[10] a) Y. Tamaru, J. Organomet. Chem.
1999, 576, 215; b) M. Kimura, A. Ezoe,
K. Shibata, Y. Tamaru, J. Am. Chem.
Soc. 1998, 120, 4033; c) M. Kimura, H.
Fujimatsu, A. Ezoe, K. Shibata, M.
Shimizu, S. Matsumoto, Y. Tamaru,
Angew. Chem. 1999, 111, 410; Angew.
Chem. Int. Ed. 1999, 38, 397; d) M.
Kimura, S. Matsuo, K. Shibata, Y. Tamaru, Angew. Chem. 1999, 111, 3586;
Angew. Chem. Int. Ed. 1999, 38, 3386;
e) M. Kimura, K. Shibata, Y. Koudahashi, Y. Tamaru, Tetrahedron Lett. 2000,
41, 6789.
[11] a) S. Ikeda, Acc. Chem. Res. 2000, 33,
511; b) S. Ikeda, H. Miyashita, M. Taniguchi, H. Kondo, M. Okano, Y. Sato, K.
Odashima, J. Am. Chem. Soc. 2002, 124,
12 060.
Angew. Chem. Int. Ed. 2003, 42, 5120 –5122
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nickell, carbonyl, compounds, bishomoallylic, alkynes, couplings, method, alcohol, allylic, catalyzed, preparation, efficiency, diener, homoallylic
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