Enatioselective synthesis of highly functionalized trifluoromethyl-bearing cyclopentenes: Asymmetric [3+2] annulation of Morita-Baylis-Hillman carbonates with trifluoroethylidenemalonates catalyzed by multifunctional thiourea-phosphines

Article abstract of DOI:10.1002/adsc.201101012

On the basis of the design and synthesis of multifunctional thiourea-phosphines, a catalytic method for the asymmetric [3+2] annulation of Morita-Baylis-Hillman carbonates with trifluoroethylidenemalonates has been developed, affording highly functionalized trifluoromethyl-bearing cyclopentenes in excellent yields, high diastereoselectivities and enantioselectivities under mild conditions. Copyright

Full text of DOI:10.1002/adsc.201101012

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DOI: 10.1002/adsc.201101012
Enantioselective Synthesis of Highly Functionalized
Trifluoromethyl-Bearing Cyclopentenes: Asymmetric
[3+2]Annulation of Morita–Baylis–Hillman Carbonates with
ACHTUNGTRENNUNG
Trifluoroethylidenemalonates Catalyzed by Multifunctional
Thiourea-Phosphines
Hong-Ping Deng,a Yin Wei,a and Min Shia,*
a
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 345 Lingling Road, Shanghai 200032, Peopleꢀs Republic of China
Fax : (+86)-21-6416-6128; e-mail: Mshi@mail.sioc.ac.cn
Received: December 25, 2011; Published online: March 13, 2012
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201101012.
Abstract: On the basis of the design and synthesis
of multifunctional thiourea-phosphines, a catalytic
method for the asymmetric [3+2]annulation of
Morita–Baylis–Hillman carbonates with trifluoro-
group. Recently, Luꢀs group applied 2,2,2-trifluoro-
AHCTUNGTREGeNNUN thylidenemalonates for asymmetric Michael addition
and Friedel–Crafts alkylation to give the desired
products in good yields with high enantioselectivi-
ties.[5,6]
ACHTUNGTRENNUNGethylidenemalonates has been developed, affording
highly functionalized trifluoromethyl-bearing cyclo-
pentenes in excellent yields, high diastereoselectivi-
ties and enantioselectivities under mild conditions.
Morita–Baylis–Hillman (MBH) adducts are useful
synthons to construct multifunctional cyclic com-
pounds because the in situ generated phosphorus
ylides from MBH adducts in the presence of tertiary
phosphines are very reactive 1,3-dipoles in a variety
of annulations.[7] Lu and co-workers first reported
a series of intra- and intermolecular [3+n]annula-
tions (n=2, 4, 6) using MBH carbonates as 1,3-di-
poles with various electron-deficient olefins catalyzed
by a tertiary phosphine, affording the corresponding
cycloadducts in good yields and high regioselectivities
under mild conditions.[8] More recently, Zhang, Huang
Keywords: asymmetric [3+2]annulation; Morita–
Baylis–Hillman carbonates; multifunctional thiour-
ea-phosphines; trifluoroethylidenemalonates; tri-
fluoromethyl-bearing cyclopentenes
Due to the unique physical properties of trifluoro- and He as well as their co-workers have also devel-
methyl-containing compounds, broad research efforts oped several MBH adducts involved in [4+1]annula-
have been focused on the strategic introduction of the tions to give the cycloaddition products in high yields,
trifluoromethyl group into drug-like molecules in me- respectively.[9]
dicinal and agricultural chemistry.[1] More specifically,
To the best of our knowledge, there are few reports
the catalytic enantioselective construction of trifluoro- about asymmetric version of this reaction. Barbas and
methyl-containing stereogenicity is still a challenge in his co-workers first reported the asymmetric intermo-
organofluorine chemistry. Scientistsꢀ efforts have been lecular [3+2]cycloaddition of MBH carbonates with
directed towards the following two aspects: (i) to di- methyleneindolinones to afford the corresponding spi-
rectly introduce a trifluoromethyl group through nu- rocyclopentane-oxindoles in good yields and high ee
cleophilic, electrophilic, or radical reactants[2,3] and (ii) values.[10] Luꢀs group developed l-threonine-derived
to exploit trifluoromethyl-containing building blocks phosphines which succeeded in catalyzing the [3+
for the construction of chiral trifluoromethyl-contain- 2]annulation of MBH carbonates with isatylidenema-
ing products.[4] This latter approach is well suited for lononitriles in high yields with high enantioselectivi-
the refinement of readily available trifluoromethyl- ties.[11] Moreover, Tang utilized spirobiindane-based
containing building blocks. 2,2,2-Trifluoroethylidene- chiral phosphines as catalysts to provide the corre-
malonates are good substrates to construct stereogen- sponding intramolecular [3+2]annulation products in
ic tertiary carbon centers bearing a trifluoromethyl good yields along with high ee values.[12]
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Hong-Ping Deng et al.
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Scheme 1. Preliminary investigations on catalyst activation for the asymmetric [3+2]annulation of trifluoroethylidenemalo-
nate 1a with MBH carbonate 2a.
Our group recently designed a series of multifunc- TP8 as catalyst, we also utilized MBH carbonates 2b
tional thiourea-phosphine catalysts derived from an and 2c instead of 2a in this reaction, and found that
axially chiral binaphthyl scaffold and have demon- 2b gave the corresponding cyclopentene 3b in 82%
strated their excellent enantioselectivities for the yield along with 9:1 dr and 90% ee (entry 9), and 2c
asymmetric aza-MBH reaction, asymmetric allylic afforded 3c with a lower ee value (entry 10). Taking
substitution of MBH adducts and moderate enantio- MBH carbonates 2d (and 2e) derived from methyl
selectivities for asymmetric [3+2]annulations of vinyl ketone (MVK) [and ethyl vinyl ketone (EVK)]
MBH carbonates with isatylidenemalononitriles.[13,14,15] as substrates, we found that TP6 was better than TP8,
In this context, we utilized the axially chiral multi- giving the corresponding product 4a (4b) in excellent
functional thiourea-phosphine A-TP as catalyst for yield, high diastereoselectivity and good ee value (en-
asymmetric [3+2]annulations of trifluoroethylidene- tries 11–13).
malonate 1a with MBH carbonate 2a to give the C-
The solvent effect was subsequently examined
1 addition product 3a in 74% yield with 33% ee using TP6 as catalyst, 1a and 2d as substrates in this
[Scheme 1, Eq. (1)]. Due to the low activity and steric reaction. The highest ee was attained in the presence
hindrance of A-TP, we designed and developed other of toluene (Table 2, entry 1). The reaction also pro-
types of multifunctional thiourea-phosphine catalyst, ceeded smoothly in other solvents to afford the de-
such as TP3 derived from l-valine, furnishing 3a in sired product 4a in good yields and good ee values,
97% yield and 78% ee [Scheme 1, Eq. (2)].[16]
Various multifunctional thiourea-phosphines, TPs, tries 3 and 4).
however THF and CH3CN led to lower ee values (en-
derived from natural amino acids were synthesized
Having determined the optimal reaction conditions
and subsequently examined for catalytic activities in for the highly stereoselective formation of functional-
the reactions of 1a with 2a in toluene at room temper- ized cyclopentenes 4, we turned our attention to the
ature for 24 h, and the results are shown in Table 1. scope of the multifunctional thiourea-phosphine-cata-
We found that TP3 was the best catalyst among the l- lyzed asymmetric [3+2]annulations of trifluoroethyli-
valine-derived multifunctional thiourea-phosphines denemalonates with MBH carbonates and the results
(Table 1, entries 1–4). Increasing the steric hindrance are summarized in Table 3. All of the reactions pro-
of multifunctional thiourea-phosphines, we consecu- ceeded smoothly under the optimal conditions, pro-
tively examined the catalysts TP5–TP7 in this reac- viding the C-1 addition products in good yields with
tion, and identified that TP6 derived from l-phenyl- excellent diastereo- and enantioselectivities. Sub-
ACHTUNGTRENNUNGalanine was the most efficient catalyst, producing 3a strates with an electron-withdrawing substituent on
in 94% yield along with 83% ee value (entries 5–7). A the aromatic ring of MBH carbonates 2 afforded the
slight structural modification of catalyst TP6 gave corresponding annulation products in excellent yields
TP8 which afforded 3a in higher ee (entry 8). Using along with high ee values (entries 1–7). Due to their
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Enantioselective Synthesis of Highly Functionalized Trifluoromethyl-Bearing Cyclopentenes
Table 1. Screening of catalysts for the asymmetric [3+2]annulation.[a]
[a]
All reactions were carried out using 1a (0.1 mmol), 2 (0.13 mmol) and catalyst
(0.02 mmol, 0.2 equiv.) in toluene (1.0 mL).
Isolated yield of major products with a dr (diastereoselective ratio) value
[b]
>99:1 if not otherwise specified.
Determined by chiral HPLC analysis.
dr=9:1.
[c]
[d]
lower activities, substrates with no or an electron-do- 1a (entries 11 and 12). Using (E)-ethyl 4,4,4-trifluoro-
nating substituent on the aromatic ring of MBH car- but-2-enoate 1d instead of 1a as the substrate in
bonates produced 4 in moderate yield and excellent above reaction, we found that no reaction occurred
ee value upon lengthening the reaction time to 48 h under the standard conditions, suggesting that
(entries 8 and 9). The MBH carbonate derived from a highly activated Michael acceptor is required in this
2-furyl aldehyde also gave the C-1 addition product 4l [3+2]annulation reaction (entry 13). To our delight,
in 78% yield along with 6.5:1 dr and 80% ee value on enlarging the reaction scale to 0.5 mmol, similar
(entry 10). Excellent results were obtained when uti- results could be obtained, affording 3a in >99% yield
lizing diethyl 2-(2,2,2-trifluoroethylidene)malonate 1b and 98:2 dr along with 92% ee (Scheme 2). The abso-
or dimethyl 2-(2,2,3,3,3-pentafluoropropylidene)malo- lute configuration of 4n has been unambiguously de-
nate 1c instead of 2,2,2-trifluoroethylidene malonate
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Hong-Ping Deng et al.
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Table 2. Solvent effects on the asymmetric [3+2]annulation of trifluoroethylidene-
malonate 1a with MBH carbonate 2a.[a]
[a]
All reactions were carried out using 1a (0.1 mmol), 2 (0.13 mmol) and catalyst
(0.02 mmol, 0.2 equiv.) in toluene (1.0 mL).
Isolated yield of major product with a dr value >99:1.
Determined by chiral HPLC analysis.
[b]
[c]
termined by X-ray analysis (see the Supporting Infor- been outlined in Scheme 3. The multifunctional thio-
mation for the details).
urea-phosphine attacks from the b-position of MBH
On the basis of above experimental results and pre- carbonate to take off carbon dioxide and tert-butyl al-
vious work,[8a,15e,17] a plausible reaction mechanism has cohol, affording phosphorus ylide I. Then the nucleo-
Table 3. Substrate scope of the asymmetric [3+2]annulation.[a]
[a]
All reactions were carried out using 1a (0.1 mmol), 2 (0.13 mmol) and catalyst
(0.02 mmol, 0.2 equiv.) in toluene (1.0 mL) for 24 h.
Isolated yield of major product with a dr value >99:1 if not otherwise specified.
Determined by chiral HPLC analysis.
Reactions were performed for 48 h.
[b]
[c]
[d]
[e]
Isolated yield of all products, dr=6.5 :1.
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Enantioselective Synthesis of Highly Functionalized Trifluoromethyl-Bearing Cyclopentenes
Scheme 2. Enlarging the reaction scale of asymmetric [3+2]annulation of 1a and 2d.
Scheme 3. A proposed mechanism.
philic attack of phosphorus ylide I to trifluoroethyli-
denemalonate with its C-1-terminal produces inter-
mediate II, which undergoes Michael addition at the
a-position of phosphorus cation to generate inter-
mediate III. The elimination of catalyst along with
the double bond formation furnishes the correspond-
ing highly functional cyclopentene product and com-
pletes the catalytic cycle. The reactivity of the in situ Scheme 4. Dihydroxylation of 3a.
generated phosphorus ylide I is crucial for the yield
of product. If the reactivity of intermediate I is not
high enough, it will partially deprotonate the NH affording 5a which bears four contiguous stereocen-
proton in multifunctional thiourea-phosphine, causing ters in 70% yield and a 25:1 dr value (Scheme 4).
the catalyst to lose activity (see Table 3, entries 8 and
In conclusion, we have developed a series of multi-
9).[18] The high regio-, diastereo- and enantioselectivi- functional thiourea-phosphines and first applied them
ty of this reaction are probably controlled by steric in the asymmetric [3+2]annulations of MBH carbo-
hindrance between benzyl group and benzhydryl nates with trifluoroethylidenemalonates, affording the
group on the catalyst with trifluoroethylidenemalo- corresponding highly functionalized trifluoromethyl-
nate as shown in Scheme 3.
or pentafluoroethyl-bearing cyclopentenes in excel-
The products of the asymmetric [3+2]annulation lent yields (up to >99%), high diastereoselectivities
can be converted into a variety of potentially useful (up to 99:1) and enantioselectivities (up to 96%)
compounds.[19] For example, the dihydroxylation of 3a under mild conditions. Current efforts are in progress
can be performed efficiently under mild conditions,[20] to use the multifunctional thiourea-phosphines in
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odology to synthesize biologically active products.
Experimental Section
General Procedure
Under an argon atmosphere, MBH carbonate 2 (0.13 mmol)
was added to a solution of trifluoroethylidenemalonate
1 (0.1 mmol), catalyst TP11 (0.02 mmol, 11 mg) in toluene
(1.0 mL) and the mixture was stirred at room temperature
for 24–48 h. The solvent was removed under reduced pres-
sure and the residue was chromatographed on silica gel (elu-
tion with petroleum ether/EtOAc=10:1–4:1) to provide
compound 3 or 4 (MBH carbonate must be added last).
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Yield: 43 mg (97%); colorless solid, mp 142–1468C; IR
(CH2Cl2): n=2957, 2925, 2852, 1739, 1606, 1522, 1435, 1348,
1
1373, 1249, 1210, 1057, 1016, 855, 843, 696 cmÀ1; H NMR
(400 MHz, CDCl3, TMS): d=1.12 (3H, t, J=7.2 Hz, CH3),
3.81 (3H, s, CH3), 3.89 (3H, s, CH3), 3.97–4.14 (3H, m,
CH+CH2), 4.54 (1H, dd, J=1.6, 7.2 Hz, CH), 6.87 (1H, d,
J=1.6 Hz, CH), 7.33 (2H, d, J=8.8 Hz, ArH), 8.19 (2H, d,
J=8.8 Hz, ArH); 13C NMR (100 MHz, CDCl3, TMS): d=
13.8, 51.0, 53.7, 54.0, 56.0 (q, J=27.5 Hz), 61.3, 66.6, 124.0,
125.4 (q, J=277.9 Hz), 128.5, 139.4, 139.9, 147.4, 147.9,
162.2, 166.8, 167.9; 19F NMR (376 MHz, CFCl3): d=À71.06
(d, J=9.4 Hz); MS (ESI): m/z (%)=463.0 (100) [M+ +
NH4]; HR-MS (MADLI): m/z=468.0866, calcd. for
C19H18NO8F3Na+1 (M+ +Na): 468.0877. The enantiomeric
excess was determined by HPLC (Chiralcel AD-H column,
l=214 nm; eluent: hexane/2-propanol=70/30; flow rate:
0.5 mLminÀ1): tmajor =12.98 min, tminor =13.89 min; ee=86%;
[a]2D0: +80.0 (c 1.0, CHCl3)].
[4] For review on the construction of trifluoromethyl-con-
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CCDC 849269 contains the supplementary crystallograph-
ic data for 4n. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
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Supporting Information
Spectroscopic data and chiral HPLC traces of the com-
pounds shown in Table 1, Table 2, Table 3, Scheme 1 and
Scheme 4 as well as detailed descriptions of the experimen-
tal procedures are available in the Supporting Information.
Acknowledgements
We thank the National Basic Research Program of China
ACHTUNGTRENNUNG(973)-2010CB833302, and the National Natural Science
Foundation of China (21072206, 20472096, 20872162,
20672127, 20821002 and 20732008) for financial support.
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