Cobalt(II)-catalyzed 1,4-addition of organoboronic acids to activated alkenes: An application to highly cis-stereoselective synthesis of aminoindane carboxylic acid derivatives

Article abstract of DOI:10.1002/chem.201202575

It all adds up: The 1,4-addition of organoboronic acids to activated alkenes catalyzed by [Co(dppe)Cl₂] is described. A [3+2]-annulation reaction of ortho-iminoarylboronic acids with acrylates to give various aminoindane carboxylic acid derivatives with cis-stereoselectivity is also demonstrated (see scheme; dppe=1,2-bis(diphenylphosphino)ethane).

Full text of DOI:10.1002/chem.201202575

DOI: 10.1002/chem.201202575
Cobalt(II)-Catalyzed 1,4-Addition of Organoboronic Acids to Activated
Alkenes: An Application to Highly cis-Stereoselective Synthesis of
Aminoindane Carboxylic Acid ACTHNUGRTENUNGDerivatives
Min-Hsien Chen, Subramaniyan Mannathan, Pao-Shun Lin, and Chien-Hong Cheng*[a]
Transition-metal-catalyzed 1,4-addition of organometallic
reagents to activated alkenes is a useful method for the effi-
cient construction of carbon–carbon bonds in organic syn-
thesis.[1] A wide range of organometallic reagents has been
commonly employed for this reaction.[2–6] Among these, or-
ganoboron reagents exhibit a multifarious advantage, com-
prising safe handling, availability, and stability to air and
moisture.[7] In this context, the rhodium-[8] and palladium-
catalyzed[9] 1,4-addition of organoboron reagents to alkenes
has received much attention due to its broad scope and high
functional-group tolerance. Particularly, extensive studies
have been devoted to rhodium-catalyzed asymmetric reac-
tions.[10] Ruthenium,[11] platinum,[12] and nickel[13] complexes
are also known to catalyze the 1,4-addition of organoborons
to a,b-unsaturated ketones. Recently, the copper-catalyzed
1,4-addition of organoboronates to alkylidene cyanoacetates
and a,b-unsaturated carbonyl compounds was also devel-
oped.[14] Despite these important developments, the use of
less expensive and more easily handled transition metals
with a wide substrate scope for the 1,4-addition reaction re-
mains in demand.
When phenylboronic acid (1a; 0.8 mmol) was treated
with n-butylacrylate (2a; 0.4 mmol) and H2O (0.8 mmol) in
a mixture of CH3CN/THF (3:1) in the presence of [Co-
AHCTUNGTREG(NNUN dppe)Cl2] (5 mol%; dppe=1,2-bis(diphenylphosphino)-
ethane) and ZnCl2 (20 mol%) at 808C for 12 h, the 1,4-addi-
tion product n-butyl-3-phenylpropanoate (3aa) was ob-
tained in 91% yield. Additionally, benzene, which is a pro-
todeboronation product of 1a, was also observed. Control
experiments revealed that in the absence of either the
cobalt complex or ZnCl2 no 3aa was observed. It is impor-
tant to mention that in our previously reported nickel-cata-
lyzed addition of boronic acids to alkenes, a Mizoroki–
Heck-type product was obtained under similar reaction con-
ditions (Scheme 1).
Recently, we reported the efficient nickel-catalyzed addi-
tions of organoboronic acids to activated alkenes[15a] and ni-
triles.[15b] We also described cobalt-catalyzed addition reac-
tions of organoboronic acids to alkynes[15c] and aldehy-
des.[15d,e] Our ongoing interest in the search for new reac-
tions that involve less expensive nickel and cobalt com-
plexes as the catalysts prompted us to use cobalt complexes
in 1,4-addition reactions.[15] Herein, we report that cobalt
can catalyze the 1,4-addition of organoboronic acids to acti-
vated alkenes, such as vinyl ketones, acrylates, acrylamides,
and acrylonitrile.[16] In addition, we have also demonstrated
a cobalt(II)-catalyzed [3+2] annulation of electron-deficient
alkenes with ortho-iminophenylboronic acids to synthesize
cis-1-aminoindane-2-carboxylic acid derivatives with high di-
astereoselectivity in good to excellent yields.
Scheme 1. Nickel- and cobalt-catalyzed 1,4-addition reactions.
To understand the present catalytic conditions, we exam-
ined the 1,4-addition reaction of 1a and 2a in the presence
of various cobalt complexes by using CH3CN as the solvent.
The dppe complex showed higher reactivity than other bi-
dentate phosphine complexes, such as 1,1-bis(diphenylphos-
phino)methane (dppm), 1,3-bis(diphenylphosphino)propane
(dppp), and 1,4-bis(diphenylphosphino)butane (dppb). Par-
ticularly, [Co
gave 3aa in 73 and 41% yield, respectively. The monoden-
tate phosphine complex [Co(PPh3)2Cl2]/3PPh3 and the bi-
dentate nitrogen–cobalt complex [Co(phen)Cl2] (phen=
ACHTUNGTRNENUG(dppe)Cl2] and [CoCAHTUNGTREN(NUGN dppe)I2] were active and
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
1,10-phenanthroline) were inactive for this 1,4-addition reac-
tion. Next, we examined the effects of additives such as
NEt3, K2CO3, and water. Of these, water exhibited the high-
est activity to give 3aa in high yield, whereas the other addi-
tives were ineffective. It is fascinating to note that in this
catalytic reaction, organoboronic acids were activated by
water instead of the base. Solvents play a vital role in the
[a] M.-H. Chen, Dr. S. Mannathan, Dr. P.-S. Lin, Prof. Dr. C.-H. Cheng
Department of Chemistry
National Tsing Hua University
Hsinchu, 30013 (Taiwan)
Fax: (+886)3572-4698
E-mail: chcheng@mx.nthu.edu.tw
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201202575.
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Chem. Eur. J. 2012, 18, 14918 – 14922

COMMUNICATION
success of the reaction. In particular, a binary solvent
system of CH3CN/THF in a ratio of 3:1 was crucial to
obtain 3aa in 91% yield. Based on these optimization stud-
ies, we chose [CoACHTUNGTRENNUNG(dppe)Cl2] (5 mol%), ZnCl2 (20 mol%),
and water (0.8 mmol) in CH3CN/THF (3:1) at 808C for 12 h
acids with a formyl group at the meta- or para-position toler-
ated the 1,4-addition reaction, providing the corresponding
products 3ea and 3 fa in impressive yields (Table 1, Entries 5
and 6). On the other hand, ortho-formyl phenylboronic
acids provided 3ga in a slightly lower yield of 65%, due to
the formation of the indene product 3ga’ by dehydration of
the indanol intermediate 3’ (Table 1, Entry 7; see also
Scheme 2). Notably, 3-nitro phenylboronic acid underwent
the addition reaction to give 3ha in 79% yield (Table 1,
Entry 8). The heteroaromatic boronic acid 1i also participat-
ed in the reaction to furnish 3ia in 86% yield (Table 1,
Entry 9). Alkenyl boronic acids were also compatible in the
reaction; (E)-1-hexenylboronic acid (1j) reacted with 2g to
give 3jg in 84% yield (Table 1, Entry 10). The para-bromo
boronic acid 1k gave 3ka in excellent yield (Table 1,
Entry 11).
This catalytic reaction was also successfully extended to
various activated alkenes (Table 1, Entries 12–16). In addi-
tion to n-butyl acrylate (2a), other acrylates such as methyl
acrylate (2b) and ethyl acrylate (2c) reacted well with 1k to
give 3kb and 3kc in excellent yields (Table 1, Entries 12 and
13). In a similar manner, other activated alkenes such as
N,N-diethyl acrylamide (2d), acrylonitrile (2e), and methyl
vinyl ketone (2 f) also gave 3kd, 3ke, and 3kf in 76, 81, and
75% yield, respectively (Table 1, Entries 14–16).
as the standard reaction conditions (Table 1).
Table 1. Results of the cobalt-catalyzed 1,4-addition reaction of arylbor-
onic acids 1 with activated alkenes 2.[a]
1
2
Product 3
Yield
[%][b]
91
1
1a 2a
3aa: R=H
(99)
75[c]
91
88
82
88
65
79
2
3
4
5
6
7
8
1b 2a
1c 2a
1d 2a
1e 2a
1 f 2a
1g 2a
1h 2a
3ba: R=2-MeO
3ca: R=3-MeO
3da: R=4-Me
3ea: R=3-CHO
3 fa: R=4-CHO
3ga: R=2-CHO
3ha: R=3-NO2
9
1i 2a
3ia
86
The proposed mechanism for the 1,4-addition reaction is
shown in Scheme 3. The catalytic reaction is probably initi-
ated by the formation of the CoII·H2O species 4 through
10 1j 2g
11 1k 2a
3jg
84
92
substitution of the coordinated chloride in [CoACTHNURGTNEUNG(dppe)Cl2] by
3ka: EWG=
CO2nBu
3kb: EWG=CO2Me 93
3kc: EWG=CO2Et
3kd: EWG=CO-
NEt2
3ke: EWG=CN
3kf: EWG=COMe
water and solvent, with the assistance of the Lewis acid
ZnCl2. Intermediate 4 then undergoes transmetallation with
phenylboronic acid (1a) to give the aryl cobalt(II) inter-
mediate 5. Coordination of n-butyl acrylate (2a) to the
cobalt center and insertion into the cobalt–aryl bond gives
the intermediate 6. Subsequent protonolysis provides the
1,4-addition product 3aa and the intermediate 4, which can
be used for further catalytic cycles.
12 1k 2b
13 1k 2c
14 1k 2d
92
76
15 1k 2e
16 1k 2 f
81
75[d]
[a] Reactions were carried out by using an arylboronic acid
(0.80 mmol), an activated alkene (0.40 mmol), [Co(dppe)Cl2]
1
2
ACHTUNGTRENNUNG
The proposed mechanism clearly explains the requirement
for a catalytic amount of the Lewis acid ZnCl2 and the role
of water in the reaction. Water not only provides the hy-
droxyl group for the arylboronic acid, but also acts as a
proton source for the formation of either the 1,4-addition
adduct 3aa or the protodeboronation product. Furthermore,
the observation of deboronation product and the absence of
biaryl compounds (ArAr) indicate that the CoII species is
not reduced.
(0.020 mmol, 5.0 mol%), ZnCl2 (0.080 mmol, 20.0 mol%), and H2O
(0.80 mmol) in MeCN/THF (3:1; 1.0 mL) at 808C for 12 h under N2.
[b] Isolated yields; the number in parentheses is the yield determined by
1H NMR spectroscopy with mesitylene as an internal standard. [c] The
reaction was carried out at 908C. [d] The reaction time was 24 h.
Under the optimized reaction conditions, various substi-
tuted arylboronic acids (1a–k) were examined (Table 1, En-
tries 1–11). The treatment of the electron-donating 2-me-
thoxy- and 3-methoxy phenyl-
boronic acids (1b and 1c, re-
spectively) with n-butyl acrylate
(2a) gave the corresponding
1,4-addition products 3ba and
3ca in 75 and 91% yield
(Table 1, Entries 2 and 3). Simi-
larly, the reaction of para-tolyl
boronic acid gave 3da in 88%
yield (Table 1, Entry 4). Elec-
tron-withdrawing
arylboronic Scheme 2. Formation of the indene byproduct 3ga’.
Chem. Eur. J. 2012, 18, 14918 – 14922
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14919

C.-H. Cheng et al.
tra and mass data. It was further supported by single-crystal
X-ray analysis (see the Supporting Information).[22] Other
cobalt catalyst systems, such as Co
(acac)2/dppe in THF/CH3CN, were also active but gave 8ah
in only 44 and 71% yield, respectively.
ACHTUNGRTEN(NGNU OAc)2/dppe and Co-
AHCTUNGTRENNUNG
To evaluate the scope of the [3+2]-annulation reaction, a
variety of ortho-iminoarylboronic acids with 2h was exam-
ined (Table 2, Entries 1–7). Thus, ortho-iminophenylboronic
acids 7b and 7c, derived from para-methoxy- and para-fluo-
roaniline, provided 8bh and 8ch in 94 and 52% yield, re-
spectively (Table 2, Entries 2 and 3). Similarly, other ortho-
iminoarylboronic acids, such as 7d–f, participated in the re-
action to provide the respective products 8dh–fh in good
yields with high stereoselectivity (Table 2, Entries 3–6).
Gratifyingly, ortho-ketoiminophenylboronic acid (7g) under-
went the annulation reaction to give 8gh in 70% yield
Scheme 3. Proposed mechanism for the cobalt-catalyzed 1,4-addition
reaction.
After successfully establishing the 1,4-addition re-
Table 2. Results of the cobalt-catalyzed [3+2] annulation of o-iminoarylboronic acids
7 with acrylates 2.[a]
action, we applied our methodology to synthesize
aminoindanes from ortho-iminoarylboronic acids
(7) and electron-deficient alkenes (2). Aminoin-
danes are valuable intermediates that are found in
various biologically active compounds.[17] Previous-
ly, metal-catalyzed [3+2]-annulation reactions for
the synthesis of indenols[18] and aminoindenes[19]
have been successfully demonstrated, but similar re-
actions for the synthesis of aminoindanes have
hardly been studied. In 2006, Takai and co-workers
reported a rhenium-catalyzed carbocyclization of
R1
R2
R3
R4
EWG
Yield
[%][b]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Me
H
H
H
H
H
H
H
p-tolyl (7a)
4-MeOC6H4 (7b)
4-FC6H4 (7c)
Me (7d)
CO2tBu (2h)
CO2tBu (2h)
CO2tBu (2h)
CO2tBu (2h)
CO2tBu (2h)
CO2tBu (2h)
CO2tBu (2h)
CO2nBu (2a)
CO2Me (2b)
CO2Et (2c)
93 (8ah)
91 (8bh)
52 (8ch)
87 (8dh)
74 (8eh)
69 (8 fh)
70 (8gh)
95 (8aa)
85 (8ab)
92 (8ac)
59 (8ad)
94 (8ai)
81 (8aj)
96 (8ak)
À
imines with acrylates by C H bond activation that
n-butyl (7e)
p-tolyl (7 f)
4-MeOC6H4 (7g)
p-tolyl (7a)
p-tolyl (7a)
p-tolyl (7a)
p-tolyl (7a)
p-tolyl (7a)
p-tolyl (7a)
p-tolyl (7a)
led to the formation of indenes instead of aminoin-
danes due to facile deamination under the harsh re-
action conditions.[20a] Later, by employing allenes as
the p-component, they synthesized substituted ami-
noindanes in high diastereoselectivity.[20b] Recently,
Tran and Cramer also reported a rhodium(I)-cata-
-O-CH2-O-
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
CONEt2 (2d)
CO2Cy (2i)
À
lyzed C H functionalization of unsubstituted ket-
CO2-2-naphthyl (2j)
CO2-PMB[c] (2k)
imines with terminal allenes leading to aminoin-
danes in
a high regio- and diastereoselective
[a] Reactions were carried out by using an ortho-iminoarylboronic acid 7 (0.30 mmol),
an activated alkene 2 (0.20 mmol), [Co(dppe)Cl2] (0.020 mmol, 10.0 mol%), K3PO4
manner.[21] These reports, however, required either
AHCTUNGTRENNUNG
higher reaction temperatures or an expensive cata- (0.20 mmol, 1.0 equiv) in MeCN (2.0 mL) at 808C for 12 h under N2. [b] Isolated
yields. [c] PMB=para-methoxybenzyl.
lyst system. Herein, we present a new and mild
cobalt-catalyzed [3+2]-annulation reaction of ortho-
iminoarylboronic acids with electron-deficient al-
kenes to give cis-1-aminoindane-2-caboxylic acid derivatives
in high regio- and diastereoselectivity.
The treatment of ortho-iminoarylboronic acid (7a) with
(Table 2, Entry 7). To further expand the scope of this pro-
tocol, we explored its compatibility with different alkenes
(Table 2, Entries 8–14). Similar to the reaction of tert-butyl
acrylate (2h), other acrylates, such as n-butyl- (2a), methyl-
(2b), ethyl- (2c), and N,N-diethyl acrylamide (2d), under-
went the [3+2]-annulation reaction to give the correspond-
ing products in high yields with excellent regio- and diaste-
tert-butyl acrylate (2h) under a [CoACTHUNRGTENUNG(dppe)Cl2]/ZnCl2/H2O
catalytic system afforded the [3+2]-annulation product 8ah
in low yield. To optimize the yield of this [3+2] annulation,
the reaction was examined under different cobalt-complex
systems (see the Supporting Information). Among these, the
AHCTUNGTREGrNNUN eoselectivity (Table 2, Entries 8–11). Likewise, 2i–k also
use of [Co
G
provided 8ai–ak in 81–96% yield respectively (Table 2, En-
tries 12–14). It is important to mention that substituted al-
kenes and cyclic enones did not react togive the 1,4-addition
or [3+2]-annulation products (3 or 8, respectively) under
the standard reaction conditions.
(1.0 equiv) as the additive in CH3CN at 808C was most
active, providing cis-aminoindane carboxylate ester (8ah) in
93% yield with high regio- and diastereoselectivity. The
structure of 8ah was confirmed by its H and 13C NMR spec-
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Chem. Eur. J. 2012, 18, 14918 – 14922

Cobalt(II)-Catalyzed 1,4-Addition of Organoboronic Acids
COMMUNICATION
The diastereochemical outcome of this [3+2]-annulation
reaction, which produces exclusively the cis-8 rather than
trans-8 product, can be predicted on the basis of the model
shown in Scheme 4, involving ortho-iminoarylboronic acid
Keywords: annulation
aminoindanes · cobalt · boron
·
1,4-addition
·
alkenes
·
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In summary, we have successfully demonstrated a cobalt-
catalyzed 1,4-addition reaction of organoboronic acids to ac-
tivated alkenes. Various types of activated alkenes, including
acrylates, acrylonitrile, acrylamide, and enones, were com-
patible with this reaction. Furthermore, a [3+2]-annulation
reaction to synthesize various cis-aminoindane carboxylic
acid derivatives was also demonstrated. The observation of
a Michael-type product and a Heck-type product in the re-
actions that use a [CoACHTUNGRTENNUG(dppe)Cl2]/ZnCl2 or [NiAHCUTGNTREN(NUGN dppe)Br2]/
ZnCl2 catalyst system, respectively, clearly reveals that the
nature of the metal complex plays a crucial role in the addi-
tion reaction of organoboronic acids with alkenes. Further
applications of the reaction in the asymmetric synthesis are
also underway.
Acknowledgements
We thank the National Science Council of the Republic of China (NSC-
99-2119-M-007-010) for support of this research.
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Received: July 19, 2012
Revised: October 8, 2012
Published online: October 30, 2012
14922
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