Asymmetric Au-catalyzed cycloisomerization of 1,6-enynes: An entry to bicyclo[4.1.0]heptene

Article abstract of DOI:10.3762/bjoc.7.116

A comprehensive study on the asymmetric gold-catalyzed cycloisomerization reaction of heteroatom tethered 1,6-enynes is described. The cycloisomerization reactions were conducted in the presence of the chiral cationic Au(I) catalyst consisting of (R)-4- M

Full text of DOI:10.3762/bjoc.7.116

Asymmetric Au-catalyzed cycloisomerization of
1,6-enynes: An entry to bicyclo[4.1.0]heptene
Alexandre Pradal, Chung-Meng Chao, Patrick Y. Toullec
and Véronique Michelet*
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2011, 7, 1021–1029.
Laboratoire Charles Friedel, UMR 7223, Ecole Nationale Supérieure
de Chimie de Paris, Chimie ParisTech, 11 rue P. et M. Curie, F-75231
Paris Cedex 05, France
doi:10.3762/bjoc.7.116
Received: 02 May 2011
Accepted: 12 July 2011
Published: 26 July 2011
Email:
Véronique Michelet* - veronique-michelet@chimie-paristech.fr
This article is part of the Thematic Series "Gold catalysis for organic
synthesis".
* Corresponding author
Keywords:
Guest Editor: F. D. Toste
asymmetric catalysis; bicycloheptene; cycloisomerization reactions;
enynes; gold
© 2011 Pradal et al; licensee Beilstein-Institut.
License and terms: see end of document.
Abstract
A comprehensive study on the asymmetric gold-catalyzed cycloisomerization reaction of heteroatom tethered 1,6-enynes is
described. The cycloisomerization reactions were conducted in the presence of the chiral cationic Au(I) catalyst consisting of (R)-4-
MeO-3,5-(t-Bu)2-MeOBIPHEP-(AuCl)2 complex and silver salts (AgOTf or AgNTf2) in toluene under mild conditions to afford
functionalized bicyclo[4.1.0]heptene derivatives. The reaction conditions were found to be highly substrate-dependent, the best
results being obtained in the case of oxygen-tethered enynes. The formation of bicyclic derivatives, including cyclopropyl pentasub-
stituted ones, was reported in moderate to good yields and in enantiomeric excesses up to 99%.
Introduction
Metal-catalyzed cycloisomerization reactions of 1,n-enynes [1-11] and the potential applications in biological active and
have emerged as efficient processes that contribute to sustain- natural products [12,13]. In 1995, Blum et al. described a novel
able development and atom economy concepts [1-8]. In the last PtCl4-catalyzed cycloisomerization reaction of allyl propynyl
ten years, they have provided extremely efficient access to ethers leading to oxabicyclo[4.1.0]heptenes [14] (Scheme 1,
cyclic skeletons with a broad range of functional moieties. reaction 1). The group of Murai observed a similar reactivity in
Among them, the synthesis of oxa- and azabi- the presence of PtCl2, although in a lower yield [15]. These
cyclo[4.1.0]heptenes starting from heteroatom-linked 1,6- seminal contributions were then followed by several compre-
enynes has been recently a field of high interest considering the hensive studies involving carbophilic complexes such as plat-
fundamental skeleton rearrangement research of 1,n-enynes inum or gold [16-22] that led to the formation of complex
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Beilstein J. Org. Chem. 2011, 7, 1021–1029.
Results and Discussion
bicyclic and tricyclic compounds [23-40]. The first asymmetric
version was described by Shibata’s group in 2005 in the pres- Optimization of the catalytic system
ence of a chiral iridium catalyst [41] (Scheme 1, reaction 2). We Based on our ongoing program on asymmetric gold catalysis
and others recently pursued the improvement and development [46,49-52], and on literature reports [53-55], we selected
of this enantioselective process, by employing platinum [42- 4-MeO-3,5-(t-Bu)2-MeOBIPHEP-(AuCl)2 complex [56-58] as
44], rhodium [45] or gold [46-48] complexes. Following our the best candidate for such a transformation. Initial experiments
previous work with chiral gold catalysts [46], we report a were performed using N-tosyl allyl substrate 1a and oxygen-
comprehensive study on gold-catalyzed enantioselective syn- linked propargylic 1,6-enyne 2a as model substrates (Table 1).
thesis of bicyclo[4.1.0]heptenes, focusing on the scope and The reaction of 1a was evaluated in various solvents and
limitations of such systems.
proceeded smoothly leading to the desired alkene 3a [59]. The
reaction kinetics and stereoselectivity were found to be highly
solvent-dependent, the enantiomeric excesses (ee) varying from
31% to 78% at room temperature (Table 1, entries 1–3). The
reaction kinetic was very slow at room temperature in ether and
toluene, but high ee’s were obtained. Increasing the tempera-
ture to 40 °C in toluene or ether had a positive effect both on the
conversion and on the ee’s (Table 1, entries 4 and 5). The reac-
tion was also conducted at 60 °C or 70 °C with good conver-
sions and ee’s (Table 1, entries 6–8), the best results being
obtained in toluene. At 80 °C in toluene, a decrease in the
stereoselectivity was observed as the ee dropped to 91%
(Table 1, entry 9). The reactivity of oxygen-tethered enynes
such as 2a was different to that for 1a as a complete conversion
was observed at room temperature in toluene, dichloromethane,
ether and tetrahydrofuran (Table 1, entries 10–13). A better ee
Scheme 1: First reports on the racemic and asymmetric synthesis of
bicyclo[4.1.0]heptenes.
Table 1: Cycloisomerization reaction of nitrogen- and oxygen-linked 1,6-enynes 1a and 2a.
Entry
Substrate
Solvent
T [°C]
t [h]
Conv. (Yield) Product
[%]a
ee [%]b
1
1a
1a
1a
1a
1a
1a
1a
1a
1a
2a
2a
2a
2a
2a
CH2Cl2
Et2O
RT
RT
RT
40
40
60
60
70
80
RT
RT
RT
RT
0
36
39
39
41
96
96
96
96
48
30
25
25
25
120
78
3a
3a
3a
3a
3a
3a
3a
3a
3a
4a
4a
4a
4a
4a
31 (−)
75 (−)
78 (−)
90 (−)
98 (−)
98 (−)
74 (−)
96 (−)
91 (−)
92 (−)
70 (−)
91 (−)
85 (−)
96 (−)
2
17
3
toluene
Et2O
11
4
28
5
toluene
toluene
THF
100 (47)
100 (74)
69
6
7
8
toluene
toluene
toluene
CH2Cl2
Et2O
100 (83)
66
9
10
11
12
13
14
100 (57)
100 (26)
100 (35)
100 (43)
100 (56)
THF
toluene
aDetermined by 1H NMR, bdetermined by HPLC.
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Beilstein J. Org. Chem. 2011, 7, 1021–1029.
Scheme 2: Synthesis of oxygen-tethered 1,6-enynes.
was obtained in toluene compared to other solvents. Cyclo- We also selected some nitrogen-tethered 1,6-enynes 1b–e from
propyl alkene 4a was isolated in 56% yield and 96% ee at 0 °C the literature [23,41-44] and synthesized them to evaluate the
in toluene (Table 1, entry 14). Toluene was therefore chosen for efficiency of the gold chiral catalytic system (Scheme 3).
further studies.
Scope and limitations of the catalytic system
Synthesis of 1,6-enynes
The prepared heteroatom-linked 1,6-enynes were then engaged
We prepared various oxygen-tethered 1,6-enynes according to in the cycloisomerization process in the presence of Au(I)
classic methodologies employing a Williamson alkylation reac- cationic catalyst generated by mixing (R)-4-MeO-3,5-(t-Bu)2-
tion and/or a Sonogashira cross-coupling [60,61] (Scheme 2 and MeOBIPHEP-(AuCl)2 complex and silver salts (Table 2).
Scheme 3). The known enyne 5 [62,63] was engaged in Anticipating the moderate reactivity of nitrogen-tethered enynes
Pd-catalyzed coupling in the presence of diversely functional- 1, the reactions were conducted at 60 °C in toluene (Table 2,
ized aryl iodides (Scheme 2). The corresponding substituted entries 1–5). The substitution of the aromatic ring on the alkyne
alkynes 2b–e [46] were isolated in 71–85% yield. An analo- moiety led to a substantial decrease of both isolated yields and
gous 1,6-enyne 6 [64] was also reacted with 3-bromoiodoben- ee’s, as the presence of several by-products was detected,
zene under the same reaction conditions and led to the forma- presumably due to degradation or polymerization [15]. A good
tion of substrate 2f in 58% isolated yield. We also envisaged ee was achieved in the case of enyne 1c, by using AgNTf2 [65]
preparing two trisubstituted alkenes 2g and 2h by an alkylation/ instead of AgOTf (Table 2, entry 2 compared to entry 1). The
Sonogashira sequence starting from commercially available substitution of the allylic side chain seemed to slow down the
substrates 7 and 8.
degradation process, as the cyclic alkene 3e was isolated in 61%
yield (Table 2, entry 4). In the case of non-substituted enyne 1b
(Table 2, entry 5), the bicyclic alkenyl derivative 3b was
isolated in low yield and ee: The synthesis of 3b was accompa-
nied by the formation of known 1,3- and 1,4-dienes (5% and
10% isolated yield respectively) resulting from 5-exo- and
6-endo cycloisomerization reactions [20,66]. Thus, the gold
catalytic system cannot compete with the results obtained for
the cyclizations of nitrogen-tethered enynes in the presence of
iridium, platinum or rhodium catalysts [41-45]. The cycloiso-
Scheme 3: Nitrogen-tethered 1,6-enynes.
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Beilstein J. Org. Chem. 2011, 7, 1021–1029.
Table 2: Cycloisomerization reaction of nitrogen- and oxygen-linked 1,6-enynes.
Entry
1c
Enyne
t [h]
Yield [%]a
Product
ee [%]b
77
1c
1c
1d
17
8
3c
3c
3d
2c,d
17
24
8
7
89
35
3c
4c
5c
1e
1b
16
16
61
23
3e
3b
13
22
6
2b
3.5
54
4b
93 (+)
7
2c
2c
15
15
25
64
4c
4c
94 (−)
94 (−)
8d
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Beilstein J. Org. Chem. 2011, 7, 1021–1029.
Table 2: Cycloisomerization reaction of nitrogen- and oxygen-linked 1,6-enynes. (continued)
9
2d
15
32
4d
96 (−)
10d
11
2d
2e
15
30
63
59
4d
4e
98 (−)
95 (−)
12
2f
1
37
4f
95 (−)
aIsolated yield, bdetermined by HPLC, c60 °C, dAgNTf2.
merization process was found to be highly stereoselective in the
case of oxygen-tethered enynes (Table 2, entries 6–12). In all
cases, the ee’s were greater than 90% and in one case as high as
98%. The stability of the resulting bicyclic alkenes 4 was gener-
ally only moderate, which led to low isolated yields. In the case
of 1,6-enynes 2c and 2d, the low yields (25% and 32% respect-
ively) could be improved by switching from AgOTf salt to
AgNTf2, presumably due to the experimentally observed lower
hygroscopicity of bistriflimide complex (Table 2, entry 7
compared to 8 and 9 compared to 10). The functionalized
derivatives 4c and 4d were obtained in 64% and 63% yields res-
pectively and in excellent ee’s (Table 2, entries 8 and 10). The
compatibility with another functional group on the aromatic
ring such as bromine (Table 2, entry 11), and with a different
allylic side chain (Table 2, entry 12) was also evaluated: The
corresponding bicyclic adducts 4e and 4f were isolated in
modest to good yield and 95% ee.
Scheme 4: Synthesis of pentasubstituted bicyclic cyclopropanes.
Conclusion
Considering the observed highly stereoselective reactions of In conclusion, we have contributed to the development of an
oxygen-tethered 1,6-enynes, we decided to study the chal- asymmetric gold-catalyzed cycloisomerization reaction
lenging asymmetric synthesis of pentasubstituted cyclopropyl allowing the formation of oxa- and aza-bicyclo[4.1.0]heptene
derivatives [67-70] (Scheme 4). The bicyclic derivative 4h was derivatives. The combination of chiral Au(I) complex (R)-4-
obtained in moderate yield and 73% ee. Conducting the reac- MeO-3,5-(t-Bu)2-MeOBIPHEP-(AuCl)2 associated to silver
tion at 0 °C and using AgNTf2 as a chloride scavenger led to the salts promotes the enantioselective rearrangement of oxygen
formation of the alkenyl functionalized derivative 4g in 36% and nitrogen-tethered 1,6-enynes in toluene at room tempera-
isolated yield and excellent 99% ee.
ture or 60 °C. The cycloisomerization reactions were found to
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Beilstein J. Org. Chem. 2011, 7, 1021–1029.
be highly substrate-dependent as low yield and ee’s were gener- synthesis of 2f, in the presence of CuI (103 mg, 0.1 equiv) and
ally obtained in the case of nitrogen-tethered enynes. The enan- PdCl2(PPh3)2 (190 mg, 0.05 equiv), 1-methoxy-4-iodobenzene
tiomerically enriched functionalized oxabicyclo[4.1.0]heptenes (1.52 g, 1.2 equiv) in distilled diisopropylamine (10 mL), (E)-
were isolated in moderate yields but with excellent ee values (2-methyl-3-(prop-2-ynyloxy)prop-1-enyl)benzene [77] (1 g, 1
ranging from 73% to 99%. This methodology was successfully equiv) was transformed to 2g (896 mg) in 57% yield. TLC
applied to the synthesis of pentasubstituted cyclopropyl hetero- (cyclohexane/ethyl acetate 90:10) Rf 0.71; 1H NMR (300 MHz,
bicycles.
CDCl3) δ 2.20 (d, J = 1.2 Hz, 3H), 4.07 (s, 3H), 4.44 (d, J = 0.9
Hz, 2H), 4.66 (s, 2H), 6.83 (s, 1H), 7.11 (m, 2H), 7.68–7.48 (m,
7H); 13C NMR (75 MHz, CDCl3) δ 15.7, 55.3, 57.8, 76.0, 83.8,
Experimental
All reactions were carried out under an argon atmosphere. 86.2, 113.9, 114.8, 126.5, 127.8, 128.1 (2C), 128.9 (2C), 133.3
1H NMR and 13C NMR were recorded on a Bruker AV 300 (2C), 134.5, 137.4, 159.7.
instrument. All signals were expressed as ppm (δ) and inter-
nally referenced to residual proton solvent signals. Coupling (E)-1-Bromo-3-(3-(2-methyl-3-phenylallyloxy)prop-1-
constants (J) are reported in Hz and refer to apparent peak ynyl)benzene (2h): Following the same procedure as for the
multiplicities. Enantiomeric excesses were determined by high synthesis of 2f, in the presence of CuI (62 mg, 0.1 equiv) and
pressure liquid chromatography analyses (HPLC) on Waters PdCl2(PPh3)2 (115 mg, 0.05 equiv), 1-bromo-3-iodobenzene
instruments (Waters 486 detector, 717 autosampler equipped (0.53 mL, 1.3 equiv) in distilled diisopropylamine (6.8 mL),
with Daicel Chiralcel OD-H, OJ and Chiralpak IA, AD, λ = 215 (E)-(2-methyl-3-(prop-2-ynyloxy)prop-1-enyl)benzene [77]
nm). Optical rotation measurements were conducted on a (611 mg, 1 equiv) was transformed to 2h (851 mg) in 76%
Perkin–Elmer 241 polarimeter at 589 nm. Enynes 5 [71], 2a yield. TLC (cyclohexane/ethyl acetate 90:10) Rf 0.63; 1H NMR
[72], 2b–e [46], 1a [73], 1b [74], 1c,d [75], 1e [73], and 6 [64] (300 MHz, CDCl3) δ 2.08 (d, J = 1.3 Hz, 3H), 4.31 (d, J = 0.8
were prepared according to published procedures. 1H, Hz, 2H), 4.53 (s, 2H), 6.71 (d, J = 1.0 Hz, 1H), 7.30 (t, J = 7.8
13C NMR and mass spectrometry data for compounds 3a,b Hz, 1H), 7.36–7.56 (m, 6H), 7.58 (dt, J = 8.0, 0.8 Hz, 1H), 7.75
[23], 3c,d [75], 3e [76] and 4a–e [46] were described elsewhere. (t, J = 1.6 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 16.0, 58.0
(2C), 85.1, 87.1, 122.5, 125.1, 127.0, 128.3, 128.5 (2C), 129.3
(E)-1-Bromo-3-(3-(3-(4-methoxyphenyl)allyloxy)prop-1- (2C), 130.1, 130.7, 132.0, 134.7, 134.9, 137.7.
ynyl)benzene (2f): CuI (46 mg, 0.1 equiv) and PdCl2(PPh3)2
(86 mg, 0.05 equiv) were placed in a Schlenk tube under argon. General procedure for Au(I)-catalyzed cycloisomerization
Distilled diisopropylamine (3 mL) was added and the reaction reactions: A mixture of L-(AuCl)2 (L = (R)-4-MeO-3,5-
mixture was stirred at RT for 5 min. 1-Bromo-3-iodobenzene (t-Bu)2MeOBIPHEP) (3 mol %) and AgOTf (or AgNTf2) (6
(0.4 mL, 1.3 equiv) was added and the reaction mixture was mol %) in distilled toluene (0.5 M) was stirred under an argon
stirred for 5 min. Enyne 6, dissolved in 2 mL of distilled diiso- atmosphere at room temperature for 30 min. Enyne (1 equiv)
propylamine was added and the reaction mixture stirred for 3 h was then added and the mixture stirred until completion of the
at RT. After hydrolysis with sat. aq. NH4Cl solution, the reaction. The mixture was then filtered through a short pad of
aqueous phase was extracted with EtOAc. The organic layer silica to eliminate the catalyst (EtOAc) and the solvents were
was successively washed with sat. aq. NH4Cl solution and concentrated under reduced pressure. The crude product was
brine. The organic layer was then dried with MgSO4, filtered purified by silica gel flash chromatography (petroleum ether/
and the solvents were evaporated under reduced pressure. The ethyl acetate 98:2 to 80:20 v/v) if necessary.
crude product was purified by silica gel chromatography (cyclo-
hexane/ethyl acetate 90:10) to give 2f as a colorless oil (509 6-(3-Bromophenyl)-7-(4-methoxyphenyl)-3-oxabi-
mg, 58%). TLC (cyclohexane/ethyl acetate 70:30) Rf 0.77; cyclo[4.1.0]hept-4-ene (4f): TLC (cyclohexane/ethyl acetate
1H NMR (300 MHz, CDCl3) δ 3.71 (s, 3H), 4.17 (dd, J = 6.3, 80:20) Rf 0.70; 1H NMR (300 MHz, CDCl3) δ 2.29 (d, J = 5.4
1.2 Hz, 2H), 4.30 (s, 2H), 6.08 (dt, J = 15.9, 6.3 Hz, 1H), 6.52 Hz, 1H), 2.65 (d, J = 6.0 Hz, 1H), 3.61 (s, 3H), 3.96 (dd, J =
(d, J = 15.9 Hz, 1H), 6.76 (d, J = 8.8 Hz, 2H), 7.07 (t, J = 7.9 10.6, 1.9 Hz, 1H), 4.30 (d, J = 10.6 Hz, 1H), 5.21 (d, J = 6.0
Hz, 1H), 7.16–7.33 (m, 3H), 7.36 (dt, J = 8.0, 1.1 Hz, 1H), 7.5 Hz, 1H), 6.18 (d, J = 6.0 Hz, 1H), 6.52–6.65 (m, 4H), 6.86–6.92
(t, J = 1.6 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 55.6, 57.9, (m, 2H), 7.12–7.19 (m, 2H); 13C NMR (75 MHz, CDCl3) δ
71.0, 85.1, 87.1, 114.4 (2C), 122.4, 123.2, 125.1, 128.1 (2C), 29.9, 30.3, 37.3, 55.5, 61.6, 111.0, 113.7 (2C), 122.5, 128.7,
129.7, 130.1, 130.7, 132.0, 133.6, 134.9, 159.8.
129.0 (2C), 129.4, 129.9, 130.1, 133.0, 141.2, 142.8, 158.2;
HPLC (Chiralpack AD, hexane/propan-2-ol (97:3), flow rate
(E)-1-Methoxy-4-(3-(2-methyl-3-phenylallyloxy)prop-1- 1.0 mL/min, λ = 215 nm): retention times 7 and 7.5 min, ee
ynyl)benzene (2g): Following the same procedure as for the 95%; [α]D23 −18.6 (c 1, CHCl3).
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Beilstein J. Org. Chem. 2011, 7, 1021–1029.
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6-(4-Methoxyphenyl)-1-methyl-7-phenyl-3-oxabi-
cyclo[4.1.0]hept-4-ene (4g): TLC (cyclohexane/ethyl acetate
90:10) Rf 0.66; 1H NMR (300 MHz, CDCl3) δ 1.18 (s, 3H),
2.84 (s, 1H), 3.73 (d, J = 10.4 Hz, 1H), 3.80 (s, 3H), 4.15 (d, J =
10.4 Hz, 1H), 5.19 (d, J = 5.8, 1 Hz, 1H), 6.21 (d, J = 5.8
Hz,1H), 6.80–6.86 (m, 4H), 7.01–7.04 (m, 2H), 7.12–7.15 (m,
3H); 13C NMR (75 MHz, CDCl3) δ 12.9, 31.6, 35.2, 38.2, 55.2,
67.8, 113.7, 114.5, 125.4, 127.5 (2C), 130.0 (2C), 130.7, 132.1
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cyclo[4.1.0]hept-4-ene (4h): TLC (cyclohexane/ethyl acetate
90:10) Rf 0.71; 1H NMR (300 MHz, CDCl3) δ 1.10 (s, 3H),
2.80 (s, 1H), 3.64 (d, J = 10.5 Hz, 1H), 4.07 (d, J = 10.5 Hz,
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J = 2.1 Hz, 1H), 6.78 (d, J = 4.0 Hz, 1H), 6.92 (dt, J = 7.7, 1.4
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13C NMR (75 MHz, CDCl3) δ 14.4, 33.2, 36.5, 39.7, 68.9,
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doi:10.1021/ja001034+
Acknowledgements
This work was supported by the Centre National de la
Recherche Scientifique and the Ministère de l’Education et de la
Recherche. Chung-Meng Chao is grateful to the Ministère de
l’Education et de la Recherche for a grant (2006–2009).
Alexandre Pradal is grateful to National Research Agency
(ANR-09-JCJC-0078) for a grant (2009–2012). The authors
thank Dr. M. Scalone (Hoffmann–La Roche) for the generous
donation of 4-MeO-3,5-(t-Bu)2-MeOBIPHEP ligand. Johnson-
Matthey is acknowledged for a generous donation of HAuCl4.
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