Enantioselective intermolecular rauhut-currier reaction of electron-deficient allenes with maleimides

Article abstract of DOI:10.1002/adsc.201100434

The 1,4-diazabicyclic[2.2.2]octane (DABCO)-catalyzed intermolecular Rauhut-Currier reaction of maleimides with electron-deficient allenes has been investigated, affording the corresponding products in good to high yields under mild conditions. The first e

Full text of DOI:10.1002/adsc.201100434

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DOI: 10.1002/adsc.201100434
Enantioselective Intermolecular Rauhut–Currier Reaction of
Electron-Deficient Allenes with Maleimides
Qian-Yi Zhao,a Cheng-Kui Pei,a Xiao-Yang Guan,a and Min Shia,b,*
a
School of Chemistry & Molecular Engineering, East China University of Science and Technology, 130 Mei Long Road,
Shanghai 200237, Peopleꢀs Republic of China
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
b
Sciences, 345 Fenglin Road, Shanghai 200032, Peopleꢀs Republic of China
Fax : (+86)-21-6416-6128; e-mail: Mshi@mail.sioc.ac.cn
Received: May 26, 2011; Published online: August 10, 2011
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adcs.201100434.
Abstract:
The
1,4-diazabicyclic
[2.2.2]octane
lecular RC reactions under mild conditions and since
then, this type of tertiary amine-catalyzed intermolec-
ular RC reactions has been further developed by Ba-
savaiah and co-workers as well as other researchers
during the last decades.[4] The first asymmetric version
of an intermolecular Rauhut–Currier reaction was
presented by Wang and co-workers using a Cinchona
alkaloid thiourea as a catalyst in a novel asymmetric
Michael–Michael cascade reaction of trans-3-(2-mer-
captophenyl)-2-propenoic acid ethyl ester with trans-
b-nitrostyrene in 2008.[5] Almost at the same time,
(DABCO)-catalyzed intermolecular Rauhut–Curri-
er reaction of maleimides with electron-deficient al-
lenes has been investigated, affording the corre-
sponding products in good to high yields under
mild conditions. The first example of a b-isocuprei-
dine (b-ICD)-catalyzed highly enantioselective in-
termolecular Rauhut–Currier reaction of male-
ACHTUNGTRENNUNGimides with allenoates and penta-3,4-dien-2-one has
been also developed, allowing the synthesis of opti-
cally active functionalized allene derivatives in
good to high yields along with good to excellent
enantioselectivities.
scandium triflate [ScACTHNUTRGNE(UGN OTf)3] combined with (R,R)-Ph-
pybox was used as a catalyst by Scheidt and co-work-
ers in an intermolecular RC reaction of silyloxyal-
lenes with a,b-unsaturated ketones, affording the cor-
responding product in 72% yield, 20:1 (Z:E) and
70% ee.[6] However, to the best of our knowledge,
there has been no report on the asymmetric intermo-
lecular RC reaction involving electron-deficient al-
kenes with allenes promoted by the amine-based or-
ganocatalyst, although enantioselective intramolecular
RC-type reactions have achieved a great progress in
Keywords: allenes; chiral g-butenolides; 1,4-
diazabicyclicACHTUNGTRENNUNG[2.2.2]octane (DABCO); enantioselec-
tivitve Rauhut–Currier reaction; b-isocupreidine (b-
ICD); maleimides
The Rauhut–Currier (RC) reaction, also known as vi- recent years.[7,8] In this paper, we would like to dis-
nylogous Morita–Baylis–Hillman (MBH) reaction, in- close the application of quinidine-derived b-isocuprei-
volves the coupling of one active alkene/latent eno- dine (b-ICD) as organocatalyst for the asymmetric in-
late to a second Michael acceptor, producing a new termolecular RC reaction of maleimides with elec-
À
C C bond between the a-position of one activated tron-deficient allenes, giving the corresponding prod-
alkene and the b-position of a second alkene under ucts in high yields and good to high ee values under
the catalysis of a nucleophilic species.[1] This reaction mild conditions.
was first reported by Rauhut and Currier in 1963 in
We initiated our investigations by seeking the best
the dimerization of electron-deficient alkenes cata- conditions for the intermolecular RC reaction be-
lyzed by tertiary phosphine.[1b] A few years later, a tween maleimide 1a and ethyl allenoate 2a. After
series of phosphine-catalyzed intermolecular RC reac- screening of the catalysts and investigating the effects
tions was subsequently explored, demonstrating the of solvent, reaction time and temperature on the reac-
wide synthetic utility of this reaction.[2] Moreover, in tion outcomes, we determined that the optimized re-
1986, Amri and Villieras[3] first disclosed that tertiary action conditions are to carry out the reaction in 1,4-
amines
such
as
1,4-diazabicyclicACTHUNGETRN[UNG 2.2.2]octane dioxane at room temperature for 3 h using DABCO
(DABCO) could also efficiently catalyze the intermo- (20 mol%) as the catalyst [Scheme 1, Eq. (a)] (see
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Scheme 1. DABCO-catalyzed RC reactions of maleimides 1
with allenes 2.
Table SI-1 in the Supporting Information for details).
Under the optimal reaction conditions, we next set
out to examine the scope and limitations of this reac-
tion using various maleimides 1 and electron-deficient
allenes 2 and it was found that all of these N-alkyl-,
N-aryl-, and N-benzyl-substituted maleimides 1 could
react with 2 smoothly to give the corresponding RC
products 3 in moderate to good yields (62–96%)
Figure 1. Nitrogen-containing
screened.
chiral
organocatalysts
Using b-ICD (20 mol%) as the catalyst, we next ex-
under the standard conditions [Scheme 1, Eq. (b)] amined the solvent effects and reaction temperature
(see Table SI-2 in the Supporting Information for de- on the reaction outcome to further optimize the reac-
tails).
tion conditions. In solvents such as CH2Cl2 (DCM),
In view of our results on the intermolecular RC re- THF, toluene, CH3CN and Et2O, the corresponding
actions of maleimides 1 with allenoates and penta-3,4- product 3aa was obtained in moderate to high yields
dien-2-one effectively catalyzed by DABCO, the next (from 68% to 96%) but with lower ee values (from
logical step was to investigate the asymmetric version 29% to 75%) (Table 1, entries 6–10). Protic solvents
of this reaction by using nitrogen-containing chiral or- such as methanol were not suitable media for this re-
ganocatalysts (Figure 1). First, quinidine and quinine action, affording complex product mixtures (Table 1,
were used as the catalysts in this RC reaction of 1a entry 11). In the mixed solvent system CH2Cl2/diox-
with 2a. We found that using quinidine (20 mol%) as ane=1:2 (v/v), 3aa was forme3d in 93% yield and
the catalyst afforded 3aa in 65% yield along with 88% ee after 24 h (Table 1, entries 3 vs. 12) and no
66% ee in 1,4-dioxane at 258C for 7 days (Table 1, improvement was observed when the reaction was
entry 1); using quinine as the catalyst, a similar result carried out at À208C (Table 1, entry 13). On further
was obtained, giving 3aa in 63% yield and 61% ee decreasing the reaction temperature to À408C and
with the reversed absolute configuration (determined using the mixed solvent system CH2Cl2/dioxane=3:2
by chiral HPLC) under the same reaction conditions (v/v), 3aa was obtained in 85% yield and up to 90%
(Table 1, entry 2). Gratifyingly, it was found that b- ee (Table 1, entry 14). Since 1,4-dioxane will freeze at
ICD was the more effective catalyst in this reaction, lower temperature in the reaction system, DCM was
giving 3aa in 93% yield and 81% ee within 16 h used as the solvent instead of 1,4-dioxane to accurate-
(Table 1, entry 3). Catalyst LB1 synthesized from b- ly examine the temperature effect. Upon decreasing
ICD by protecting the OH group with tert-butyl- the reaction temperature from to 08C to À208C or
(diphenyl)chlorosilane (TBDPSCl) could not catalyze À408C, we found that 3aa could be obtained in up to
this reaction under the standard conditions, suggesting 92% yield and 96% ee when the reaction was carried
that the C-6’-OH group of b-ICD is very important out at À208C within 24 h (Table 2, entries 15–17). Re-
for the reaction (Table 1, entry 4). Another Cinchona ducing the employed amount of b-ICD from 20 mol%
alkaloid-derived catalyst LB2 was also examined in to 10 mol% or 5 mol% resulted in the same reaction
this reaction, giving 3aa in 92% yield and 71% ee outcomes (Table 1, entries 18 and 19). Therefore, the
within one day (Table 1, entry 5).
best reaction conditions have been identified as those
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Enantioselective Intermolecular Rauhut–Currier Reaction of Electron-Deficient Allenes
Table 1. Optimization of the reaction conditions in the asymmetric RC reaction of 1a
with 2a.[a]
[a]
The reaction was carried out on a 0.15 mmol scale, and the ratio of 1/2 was 1.0/2.0.
Isolated yields.
Determined by chiral HPLC.
10 mol% b-ICD was used.
[b]
[c]
[d]
[e]
5 mol% b-ICD was used.
using 5 mol% of b-ICD as the catalyst and carrying action should be carried out at À608C in DCM for
out the reaction in CH2Cl2 at À208C for 24 h.
72 h, affording the corresponding products 3qq–3yy in
With these optimal reaction conditions in hand, we
subsequently turned our attention to examine the sub-
strate scope of this interesting asymmetric RC reac-
tion with respect to a variety of maleimides and elec-
tron-deficient allenes. The results of these experi-
ments are summarized in Table 2. As can be seen
from Table 2, N-benzylmaleimide 1a and a variety of
N-benzylmaleimide derivatives 1b–1i having electron-
rich or electron-poor aromatic groups on their R1
groups or N-2-thienylmethylmaleimide 1j bearing a
heteroaromatic group as its R1 group could react with
electron-deficient allenes 2a, 2b and 2d smoothly to
give the corresponding RC products 3bb–3pp in good
to high yields along with 91–98% enantiomeric ex-
cesses (Table 2, entries 1–16). In the cases of male-
ACHTUNGTRENNUNG
imides 1k–1r in which R1 are aromatic groups, the re- Figure 2. ORTEP drawing of 3ww.
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Qian-Yi Zhao et al.
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Table 2. Substrate scope of the asymmetric RC reaction of maleimides 1 with electron-defi-
cient allenes 2 catalyzed by b-ICD[a]
.
[a]
The reaction was carried out on a 0.15-mmol scale with 5 mol% b-ICD under Ar in
CH2Cl2 (1.0 mL) at À208C for 24 h and the ratio of 1/2 was 1.0/2.0.
Isolated yields.
Determined by chiral HPLC analysis.
Absolute configuration was determined by X-ray diffraction of 3ww (see the Supporting
Information).
[b]
[c]
[d]
[e]
[f]
The reaction was carried out at À608C for 72 h.
The yields and ee values were obtained by carrying out the reactions at À208C for 24 h.
The ee value in the parenthesis was that of 3ww after a single recrystallization.
[g]
68–91% yields and 72–85% ee values (Table 2, en- enantiomeric excesses at À608C (Table 2, entries 26–
tries 17–25). A single recrystallization of 3ww with 29). The relatively lower yields and enantiomeric ex-
85% ee from DCM/petroleum ether (1:4) afforded cesses for entries 17–29 in Table 2 were presumably
the corresponding product in nearly enantiomeric due to the electronic and steric effects of N-aryl- or
pure product (99% ee), indicating that a simple re- N-alkylmaleimides 1k–1u.
crystallization can improve the enanatiomeric excess
The absolute configuration of products 3 or 4 was
of the obtained product (Table 2, entry 23). As for N- unambiguously assigned as the S-configuration on the
H maleimide 1s, as well as the N-alkylmaleimide de- basis of the X-ray crystallographic analysis of product
rivatives 1t and 1u, the reactions also proceeded 3ww which has two bromine atoms on the aromatic
smoothly to give the corresponding RC products 3zz ring (Figure 2).
and 4aa–4cc in 68–86% yields along with 73–81%
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Enantioselective Intermolecular Rauhut–Currier Reaction of Electron-Deficient Allenes
Scheme 2. Further transformation of the obtained chiral Rauhut–Currier reaction products 3aa and 3nn.
To illustrate the synthetic utility of the thus ob- the major stereoisomer has been indicated in
tained optically active RC reaction products 3 or 4, Scheme 3, leading to the production of the desired
the further transformation of 3aa or 3nn was per- isomer D, which is then isomerized to intermediate E.
formed in the presence of transition metal catalysts Finally, intermediate E undergoes b-elimination to
(Scheme 2). As shown in Scheme 2, the FeCl3/PdCl2- afford the RC adduct 3 or 4 and regenerate b-ICD at
cocatalyzed coupling cyclization[9] of optically active the same time to complete the catalytic cycle.
RC product 3aa (96% ee) with allylic bromide afford-
In summary, we have developed an efficient
ed the corresponding b-allylic substituted g-buteno- DABCO-catalyzed intermolecular Rauhut–Currier re-
lide derivative 5 in 84% isolated yield with ee value action of maleimides with electron-deficient allenes to
retained. Optically active product 3nn could be also afford the corresponding products in good to high
readily transformed into the corresponding function- yields under mild conditions. Furthermore, the first
alized furan derivative 6 in 99% yield with ee value example of the highly enantioselective intermolecular
retained in acetonitrile by the silver-catalyzed rear- Rauhut–Currier reaction of maleimides with alle-
rangement of the allenic moiety.[10] Furthermore, iso- noates and penta-3,4-dien-2-one has also been dis-
merization of product 3 catalyzed by PPh3 has been closed to produce the corresponding functionalized
also performed in toluene and the result has been allenic derivatives in good to high yields along with
summarized in Scheme SI-1 in the Supporting Infor- good to excellent enantioselectivities in the presence
mation.
of b-ICD (5 mol%) in CH2Cl2 at À208C or À608C.
Based on the above experimental findings and pre- These chiral functionalized allenic derivatives can be
vious mechanistic studies,[11] we propose a plausible further transformed to the corresponding chiral g-bu-
mechanism of b-ICD-catalyzed asymmetric RC reac- tenolide derivatives and furan derivatives in good
tion in Scheme 3. The enolate A is generated upon yields in the presence of transition metal catalysts.
nucleophilic addition of b-ICD to the allenic sub-
strate, which is stabilized by the C-6’-OH group of b-
ICD via an intramolecular hydrogen bonding interac-
tion. The subsequent 1,4-addition of A with malei-
mide 1 leads to the formation of zwitterionic inter-
Experimental Section
mediate B. The following proton transfer is the key
step (rate-determining step) on the basis of previous
literature.[12] We believe that the acidic proton of the
C-6’-OH group serves as a “proton shuttle” to facili-
tate the intramolecular proton transfer from the a-
carbon to the oxygen anion. A plausible transition-
state model C indicating the favorable key proton
transfer step via intramolecular proton relay is also
shown in Scheme 3. This proton transfer step also
General Procedure for the DABCO- or b-ICD-
Catalyzed Intermolecular Rauhut–Currier Reaction
of Maleimide 1 with Electron-deficient Allene 2
Maleimide 1 (0.15 mmol), allene 2 (0.30 mmol), DABCO
(0.030 mmol) or b-ICD (0.0075 mmol), and 1,4-dioxane or
dichloromethane (1.0 mL) were added into a Schlenk tube.
The reaction mixture was stirred at room temperature for
3 h or at À208C for 24 h, the solvent was removed under re-
duced pressure, and the residue was purified by flash
likely differentiates the four diastereomers of B and column chromatography (PE/EA=4/1–2/1).
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Qian-Yi Zhao et al.
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Scheme 3. A plausible mechanism.
References
Supporting Information
Experimental procedures, chiral HPLC traces, and spectro-
scopic data for all new compounds, X-ray crystal structure
and CIF data for 3ww are available in the Supporting Infor-
mation.
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Adv. Synth. Catal. 2011, 353, 1973 – 1979
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asc.wiley-vch.de
1979