Regioselective hydroacylation of 1,3-dienes by cobalt catalysis

Article abstract of DOI:10.1021/ja500268w

We describe a cobalt-catalyzed hydroacylation of 1,3-dienes with non-chelating aldehydes. Aromatic aldehydes provide 1,4-addition products as the major isomer, while aliphatic aldehydes favor 1,2-hydroacylation products. The kinetic profile supports an oxidative cyclization mechanism involving a cobaltacycle intermediate that undergoes transformation with high regio- and stereoselectivity.

Full text of DOI:10.1021/ja500268w

Communication
pubs.acs.org/JACS
Regioselective Hydroacylation of 1,3-Dienes by Cobalt Catalysis
Qing-An Chen, Daniel K. Kim, and Vy M. Dong*
Department of Chemistry, University of California, Irvine, 4403 Natural Sciences 1, Irvine, California 92697, United States
S
* Supporting Information
Scheme 1. Proposed Cobalt-Catalyzed Hydroacylation of
Dienes by Oxidative Cyclization
ABSTRACT: We describe a cobalt-catalyzed hydroacylation
of 1,3-dienes with non-chelating aldehydes. Aromatic
aldehydes provide 1,4-addition products as the major isomer,
while aliphatic aldehydes favor 1,2-hydroacylation products.
The kinetic profile supports an oxidative cyclization mec-
hanism involving a cobaltacycle intermediate that undergoes
transformation with high regio- and stereoselectivity.
modern challenge in organic synthesis is the invention of
methods that use catalysts derived from first-row transition
A
metals.1 A number of valuable olefin transformations, including
hydrogenation,2 hydroformylation,3 and hydrovinylation,4 have
been achieved by cobalt catalysis. These breakthroughs highlight
Co as an attractive and complementary alternative to Rh due
to its relatively low cost and high abundance. Encouraged by
this progress, we recently turned our attention to developing
olefin hydroacylation5−14 by cobalt catalysis.15 Brookhart
demonstrated the first and only previously known intermolecular
Co-catalyzed hydroacylation (eq 1).15a,b While promising, this
1 and a 1,3-diene 2.17 The resulting cobaltacycle B exists in two
η1 forms: seven-membered cobaltacycle C and five-membered
cobaltacycle C′.4,18,19 Depending on the substrate and ligand,
cobaltacycle C or C′ would undergo transformation by Path I or
II, respectively. A β-hydride elimination generates intermediate
D or D′, which can undergo reductive elimination to yield
product 3 or 3′ and regenerate catalyst A. In Path I, formation of
the cobaltacycle intermediate requires a cis-olefin geometry; thus,
we propose this pathway would lead to the Z-isomer of 3 with
high levels of stereocontrol.
To test our hypothesis, we chose benzaldehyde 1a and
isoprene 2a as model substrates. Control experiments confirm
that these substrates are unreactive in the absence of either
Co(II) salts or reducing agents.20 We then examined the
transformation using Co(II) (a catalyst precursor for hydro-
vinylation)4 with various ligands and additives to generate the
requisite Co(I) catalyst. A survey of 20 commercially available
phosphines reveals 1,3-bis(diphenylphosphino)propane (dppp)
is the most promising ligand. With Co(II)-dppp, the desired
product is observed in 11% yield by using Zn/ZnI2, a known
protocol for generating Co(I) (Table 1, entry 1).4,16 By applying
In as the reductant instead, we observe improved reactivity (21%,
entry 2). Through a further survey of additives, we find that a
combination of In/InBr3 gives the best result (57% yield, entries
3−5). Given the role of ZnI2 in hydrovinylation,4 we assume
InBr3 similarly promotes the formation of cationic Co(I) species.
In the absence of these Lewis acids, the yield is diminished
(13% yield, entry 6). In all cases, we observe the β,γ-unsaturated
ketone in preference to the γ,δ-unsaturated ketone (up to 19:1
selectivity). In accordance with our proposed mechanism, the
strategy was limited to vinylsilanes, and aldehyde decarbonyl-
ation remained competitive. We imagined developing a Co(I)-
catalyzed cross-coupling of various aldehydes and 1,3-dienes
(eq 2). Our C−H bond functionalization would yield β,γ- and/or
γ,δ-unsaturated ketones with high regioselectivity and excellent
atom economy. Moreover, this proposed hydroacylation would
afford regiocontrol distinct from current technologies, including
the relevant Ru-catalyzed pathway developed independently by
Krische11c and Ryu11d (eq 3).
Our proposal draws from a mechanism established by Hilt
for the Co-catalyzed hydrovinylation of olefins to generate
1,4-dienes.4 As shown in Scheme 1, a Co(II) precatalyst can be
used to generate the Co(I) catalyst.16 We hypothesize that Co(I)
catalyst A would promote oxidative cyclization between aldehyde
Received: January 9, 2014
Published: March 3, 2014
© 2014 American Chemical Society
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Communication
a
a
Table 1. Additives Effects for Hydroacylation
Table 3. Variation in the Aldehyde Scope
b
c
c
entry
R in 1
Ph (1a)
yield (%)
3/3′
Z/E (3)
b
c
c
entry
additives
yield (%)
3aa/3aa′
Z/E (3aa)
1
2
3
4
5
6
7
8
87
92
96
60
78
88
90
97
83
64
89
94
94
86
17
82
78
83
91
74
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
2:1
19:1
>20:1
>20:1
>20:1
>20:1
>20:1
6:1
1
2
3
4
5
6
Zn/ZnI2
In/ZnI2
In/InI3
In/InBr3
In/InCl3
In/
11
21
45
57
28
13
12:1
14:1
17:1
19:1
14:1
13:1
10:1
16:1
13:1
11:1
17:1
18:1
4-BrC6H4 (1b)
4-ClC6H4 (1c)
4-FC6H4 (1d)
4-CF3C6H4 (1e)
4-MeO2CC6H4 (1f)
4-MeC6H4 (1g)
4-MeOC6H4 (1h)
4-MeOC6H4 (1h)
3-BrC6H4 (1i)
3-ClC6H4 (1j)
2-furyl (1k)
a
1a (0.20 mmol), 2a (0.60 mmol), Co(dppp)I2 (5 mol%), In or Zn
(20 mol%), MXn (5 mol%), DCE (1 mL), 60 °C, 24 h. Overall yield
of 3aa and 3aa′, determined by H NMR or GC-FID with dimethyl
terephthalate (0.05 mmol) as internal standard. Determined by H
NMR or GC-FID.
2:1
b
d
9
11:1
>20:1
>20:1
>20:1
6:1
1
10
11
12
13
14
15
c
1
2-naphthyl (1l)
(E)-styryl (1m)
Cy (1n)
a
Table 2. Ligand Effects of DPPP Analogues
6:1
n/a
e
16
Cy (1n)
1:8
n/a
e
17
n-C5H11 (1o)
n-C6H13 (1p)
n-C7H15 (1q)
BnCH2 (1r)
1:5
n/a
e
18
e
1:4
n/a
19
1:5
n/a
e
20
1:4
n/a
a
1 (0.20 mmol), 2a (0.60 mmol), Co(L6)I2 (5 mol%), In (10 mol%),
b
b
c
c
entry
catalyst
yield (%)
3aa/3aa′
Z/E (3aa)
InBr3 (5 mol%), DCE (0.5 mL), 60 °C, 20−24 h. Isolated yield of all
c
isomers. Determined by GC-FID or 1H NMR; trace amount of
1
2
3
4
5
6
7
Co(dppp)I2
Co(L1)I2
Co(L2)I2
Co(L3)I2
Co(L4)I2
Co(L5)I2
Co(L6)I2
Co(L6)I2
57
59
63
50
83
95
19:1
17:1
11:1
17:1
13:1
15:1
6:1
product 4 was observed as minor isomer (3/4 >20:1) for aldehydes
d
e
1a−m. DCE/toluene (1:1, 0.5 mL) was used solvent. 1 (0.20 mmol),
2a (0.60 mmol), Co(dcpe)I2 (5 mol%), In (20 mol%), InBr3 (5 mol%),
DCE/EtOAc (3:1, 0.5 mL), 50 °C, 20−24 h.
19:1
14:1
>20:1
>20:1
>20:1
>20:1
3:1
competitive olefin isomerization. The use of a mixed solvent
(1:1 DCE/toluene) presumably inhibits isomerization and
allows isolation of the desired product in good yield and higher
stereoselectivity (11:1, entry 8 vs 9). This catalyst promotes
hydroacylation of heteroaromatic aldehyde 1k (94% yield,
entry 12). Moreover, the hydroacylation of isoprene 2a with
α,β-unsaturated aldehyde 1m provides a conjugated ketone in
86% yield and >20:1 regioselectivity (entry 14).
83
20:1
19:1
d
e
8
91 (87 )
a
1a (0.20 mmol), 2a (0.60 mmol), Co(II) (5 mol%), In (20 mol%),
b
InBr3 (5 mol%), DCE (1 mL), 60 °C, 24 h. Overall yield of 3,
determined by 1H NMR or GC-FID with dimethyl terephthalate
c
(0.05 mmol) as internal standard. Determined by 1H NMR or GC-FID.
d
e
In (10 mol%), DCE (0.5 mL). Isolated yield.
With catalyst Co(L6)I2, aliphatic aldehyde 1n is less reactive
and undergoes hydroacylation with lower regioselectivity
(Table 3, entry 15). Toward addressing this challenge, we
investigated a range of parameters and found promising reactivity
with a more electron-rich phosphine ligand, 1,2-bis(dicyclohexyl-
phosphino)ethane (dcpe).20 The resulting ketone products are
obtained in good yields with a dramatic switch in regiocontrol
(entry 15 vs 16). Generally, the 1,2-hydroacylation products 3′
are afforded as the major isomer with regioselectivities ranging
from 4:1 up to 8:1 for aliphatic aldehydes 1n−r (entries 16−20).
In these cases, we observe high C1-regioselectivity (C−C bond
formation at 1-position of diene 1a) instead of C3-regio-
selectivity (eq 2 vs 3).
Next, we examined the scope of dienes (Table 4). For
benzaldehyde, high yields (77−97%) and excellent regio- and
stereoselectivities (>20:1 for both) are achieved for hydroacyl-
ation of 2-aryl-substituted butadienes, despite varying electronic
and steric properties of substituents (entries 1−9). The catalyst
loading can be reduced to 2 mol% for the coupling of
benzaldehyde 1a and 2-phenylbutadiene (entry 2). The use of
2-cyclohexylbutadiene gives β,γ-unsaturated ketone 3aj with
stereochemistry of the resulting trisubstituted olefin is Z, as
confirmed by 2D NOESY analysis.
To tune the catalyst, we prepared six analogues of dppp by
varying the substitution pattern on the aryl groups (L1−L6,
Table 2). From this study, we find that L6 (where Ar = 3,4-
(MeO)2C6H3) gives high yield, regioselectivity, and stereo-
control (87% isolated yield, >20:1 regioselectivity, and 19:1 Z/E,
entry 8). With L6, the amount of In powder can be reduced to
10 mol% (entry 8). A trace amount of γ,δ-unsaturated ketone 4aa
is observed as a minor product (3aa/4aa >20:1, entry 8). Our
cobalt catalyst favors the 1,4-hydroacylation product 3aa over the
1,2-addition isomer 5aa which has been accessed with Ru(II)
catalysis.11c,d Thus, cobalt enables a rare type of hydroacyla-
tion that occurs across a conjugated π-system rather than a single
π-bond.
With this protocol in hand, we explored the hydroacylation of
diene 2a using 18 different aldehydes (Table 3). In general, good
to high yields are obtained with various aromatic aldehydes 1
(60−97% yields, entries 1−13). In the case of electron-rich aryl
aldehyde 1h, we observe a drop in stereoselectivity (2:1) due to
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a
Table 4. Variation of the Diene Partner
4-position of diene 2b without any detectable deuterium at other
positions (eq 9). This result suggests that the hydroacylation
with aromatic aldehydes proceeds through a 1,4-addition
pathway (Path I, Scheme 1). For hydroacylation with aliphatic
aldehyde d-1r, the deuterium atom is incorporated completely at
the β- and δ-position of products d-3rb′ and d-3rb, respectively
(eq 10). While further studies are warranted, our observations
support a mechanistic proposal where Path I or II is favored
(Scheme 1), depending on the properties of both the ligand and
the substrate.
In contrast to the traditional mechanism of hydroacylation
catalyzed by Rh(I) or Co(I), we propose an oxidative cyclization
mechanism that avoids decarbonylation. Our catalyst promotes
C1-regioselective hydroacylation of dienes and can be tuned
to favor either 1,4- or 1,2-hydroacylation. Through the 1,4-
hydroacylation pathway, we achieve the stereoselective synthesis
of trisubstituted olefins, which are key building blocks that are
challenging to access.24 Ongoing efforts will focus on studying
other catalysts for achieving higher selectivities and greater scope.
Our study contributes to the emerging strategies available for
hydroacylation via non-precious-metal catalysis.13,15
a
1 (0.30 mmol), 2 (0.20 mmol), Co(L6)I2 (5 mol%), In (10 mol%),
InBr3 (5 mol%), DCE (0.5 mL), 60 °C, 16 h. Only one isomer was
ASSOCIATED CONTENT
* Supporting Information
Experimental details and kinetic data. This material is available
free of charge via the Internet at http://pubs.acs.org.
observed, except for 3aj (E/Z 6:1). The geometry of 3ab and 3ak was
■
b
assigned by NOESY spectra. Co(L6)I2 (2 mol%).
S
moderate stereoselectivity (6:1) and good yield (87%, entry 10).
Hydroacylation of a 1,2-disubstituted diene occurs with moderate
yield (entry 11),21 while 2-phenylbutadiene 2b couples well with a
variety of aldehydes (entries 12−17). Throughout these studies,
we observe no aldehyde decarbonylation, the byproduct expected
for hydroacylations involving C−H bond activation of non-
chelating aldehydes.
AUTHOR INFORMATION
Corresponding Author
vy.dong@uci.edu
Notes
■
The authors declare no competing financial interest.
Finally, we report mechanistic studies that further support our
proposed oxidative cyclization mechanism, in preference to a
C−H activation pathway.15a,b First, a kinetic isotope effect (KIE,
kH/kD) of 2.7 is observed from competition experiments between
benzaldehyde 1a and d-1a (eq 8).22 If hydroacylation occurs
through a traditional C−H activation mechanism, either oxidative
addition of Co(I) to the aldehyde or insertion of the diene into
the Co−H will be the turnover-limiting step.5d However, we
observe a zero-order dependence on both aldehyde and diene
concentrations,20,23 thus disfavoring a C−H activation pathway.
The KIE is consistent with β-hydride or reductive elimination as
the turnover-limiting step in Path I (Scheme 1).22 Moreover, the
zero-order dependence on both the aldehyde and the diene
concentrations supports the possibility of metallacycle C or D as
catalyst resting state (Scheme 1).
ACKNOWLEDGMENTS
■
Funding was provided by UC Irvine and the National Institutes
of Health (GM105938). V.M.D. is grateful to Eli Lilly for a
Grantee Award.
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(a) Kokubo, K.; Matsumasa, K.; Miura, M.; Nomura, M. J. Org. Chem.
1997, 62, 4564. (b) Tanaka, K.; Fu, G. C. J. Am. Chem. Soc. 2001, 123,
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Ed. 2002, 41, 2146. (d) Tanaka, K.; Fu, G. C. J. Am. Chem. Soc. 2002,
124, 10296. (e) Lee, D. Y.; Hong, B. S.; Cho, E. G.; Lee, H.; Jun, C. H. J.
Am. Chem. Soc. 2003, 125, 6372. (f) Tanaka, K.; Fu, G. C. J. Am. Chem.
135, 3796. (i) Koepfer, A.; Sam, B.; Breit, B.; Krische, M. J. Chem. Sci.
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2013, 4, 1876. (j) Park, B. Y.; Montgomery, T. P.; Garza, V. J.; Krische,
M. J. J. Am. Chem. Soc. 2013, 135, 16320.
(18) For selected cobaltacycle-promoted reactions, see: (a) Chang, H.-
T.; Jayanth, T. T.; Cheng, C.-H. J. Am. Chem. Soc. 2007, 129, 4166.
(b) Jeganmohan, M.; Cheng, C.-H. Chem.Eur. J. 2008, 14, 10876.
(c) Wong, Y.-C.; Parthasarathy, K.; Cheng, C.-H. J. Am. Chem. Soc. 2009,
131, 18252. (d) Wei, C.-H.; Mannathan, S.; Cheng, C.-H. J. Am. Chem.
Soc. 2011, 133, 6942. (e) Wei, C.-H.; Mannathan, S.; Cheng, C.-H.
Angew. Chem., Int. Ed. 2012, 51, 10592.
(19) Similar metallacycles have been observed in Ni(0)- or Ru(0)-
catalyzed cross-coupling of dienes; see refs 17g−i.
(20) For more details, see Supporting Information.
(21) For 2,3-dimethyl-1,3-butadiene, the desired hydroacylation
product was obtained in high regioselectivity (>20:1) but with low
yield (19%). No coupling product was observed in the hydroacylation of
1,3-cyclohexadiene with benzaldehyde.
(22) Simmons, E. M.; Hartwig, J. F. Angew. Chem., Int. Ed. 2012, 51,
3066.
(23) Blackmond, D. G. Angew. Chem., Int. Ed. 2005, 44, 4302.
(24) Negishi, E. I.; Huang, Z. H.; Wang, G. W.; Mohan, S.; Wang, C.
Acc. Chem. Res. 2008, 41, 1474.
́
Soc. 2003, 125, 8078. (g) Gonzalez-Rodríguez, C.; Pawley, R. J.;
Chaplin, A. B.; Thompson, A. L.; Weller, A. S.; Willis, M. C. Angew.
Chem., Int. Ed. 2011, 50, 5134. (h) Lenden, P.; Entwistle, D. A.; Willis,
M. C. Angew. Chem., Int. Ed. 2011, 50, 10657.
(8) For Rh-catalyzed hydroacylation of allenes, see: Osborne, J. D.;
Randell-Sly, H. E.; Currie, G. S.; Cowley, A. R.; Willis, M. C. J. Am. Chem.
Soc. 2008, 130, 17232.
(9) For Rh-catalyzed intramolecular hydroacylation of dienes, see:
Sato, Y.; Oonishi, Y.; Mori, M. Angew. Chem., Int. Ed. 2002, 41, 1218.
(10) For Rh-catalyzed hydroacylation of ketones, see: (a) Shen, Z.;
Khan, H. A.; Dong, V. M. J. Am. Chem. Soc. 2008, 130, 2916. (b) Phan,
D. H. T.; Kim, B.; Dong, V. M. J. Am. Chem. Soc. 2009, 131, 15608.
(c) Shen, Z.; Dornan, P. K.; Khan, H. A.; Woo, T. K.; Dong, V. M. J. Am.
Chem. Soc. 2009, 131, 1077. (d) Khan, H. A.; Kou, K. G. M.; Dong, V. M.
Chem. Sci. 2011, 2, 407.
(11) For selected Ru-catalyzed hydroacylations, see: (a) Kondo, T.;
Akazome, M.; Tsuji, Y.; Watanabe, Y. J. Org. Chem. 1990, 55, 1286.
(b) Kondo, T.; Hiraishi, N.; Morisaki, Y.; Wada, K.; Watanabe, Y.;
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