Zirconoarylation of alkynes through p-chloranilpromoted reductive elimination of arylzirconates

Article abstract of DOI:10.3762/bjoc.10.48

A novel method for the zirconoarylation of alkynes was developed. TCQ-promoted reductive elimination of arylzirconate [LiCp₂ZrAr(RC=CR) ], which was prepared by the reaction of zirconocene-alkyne complexes with aryllithium compounds, afforded trisubstituted alkenylzirconocenes. This reaction can afford multi-substituted olefins with high stereoselectivity.

Full text of DOI:10.3762/bjoc.10.48

Zirconoarylation of alkynes through p-chloranil-
promoted reductive elimination of arylzirconates
Xiaoyu Yan1, Chao Chen1 and Chanjuan Xi*1,2
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2014, 10, 528–534.
1Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical
Biology (Ministry of Education), Department of Chemistry, Tsinghua
University, Beijing 100084, China and 2State Key Laboratory of
Elemento-Organic Chemistry, Nankai University, Tianjin 300071,
China
doi:10.3762/bjoc.10.48
Received: 30 October 2013
Accepted: 07 February 2014
Published: 28 February 2014
Email:
This article is part of the Thematic Series "Multicomponent reactions II".
Guest Editor: T. J. J. Müller
Chanjuan Xi* - cjxi@tsinghua.edu.cn
* Corresponding author
© 2014 Yan et al; licensee Beilstein-Institut.
License and terms: see end of document.
Keywords:
alkyne; multicomponent; reductive elimination; zirconate;
zirconoarylation
Abstract
A novel method for the zirconoarylation of alkynes was developed. TCQ-promoted reductive elimination of arylzirconate
[LiCp2ZrAr(RC≡CR)], which was prepared by the reaction of zirconocene–alkyne complexes with aryllithium compounds,
afforded trisubstituted alkenylzirconocenes. This reaction can afford multi-substituted olefins with high stereoselectivity.
Introduction
The controlled synthesis of multi-substituted olefins is one of alkynes. The newly formed carbon–metal bond can be used for
the most challenging tasks in organic synthesis [1,2]. A series of further synthetic transformation toward multi-substituted olefins
reactions have been developed for the construction of substi- [24-36] (Scheme 1, route d).
tuted olefins. Among them, an important route is the addition of
various reagents to nonactivated alkynes to form substituted A large number of carbometalation reactions of alkynes have
olefins. For example, semihydrogenation of internal alkynes can been reported. Most of the carbometal reagents, which were
afford disubstituted olefins (Scheme 1, route a) [3-5]. Hydrocar- used, contained Li, Mg, Cu, Zn, B, or Al [12-16]. In the last
bonation [6,7] and hydrometalation/functionalization [8-11] of several decades also zirconium-mediated or -catalyzed organic
internal alkynes can afford trisubstituted olefins (Scheme 1, reactions have been extensively investigated [37-39]. In addi-
routes b and c), respectively. The most exciting progress was tion, a series of organic reactions using zirconocene species
the carbometalation of internal alkynes [12-23], which involves have been reported, in particular for the reductive coupling of
simultaneous addition of a metal atom and an organic residue to alkenes or alkynes with other unsaturated compounds [40-43].
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Beilstein J. Org. Chem. 2014, 10, 528–534.
alkyne. Herein we describe the TCQ-promoted reductive elimi-
nation of arylzirconate to afford an arylzirconation product of
the alkyne, which can be converted to multi-substituted olefins
through coupling with electrophiles (Scheme 3).
Results and Discussion
Initially, the reaction of Cp2Zr(PhC≡CPh)(DMAP) (1a),
prepared by the reaction of Cp2ZrBu2 [48] with DMAP and di-
phenylacetylene according to reported literature [49], with
phenyllithium produced arylzirconate 2a. To this mixture,
2 equivalents of p-chloranil (TCQ) were added and the reaction
mixture was stirred for 12 h at room temperature. After being
quenched with HCl solution, the desired triphenylethylene (3a)
was isolated in 62% yield. When the reaction mixture was
quenched with DCl solution, the deuterated product 3a-D was
isolated in 60% yield with >95% of deuterium incorporation
(Scheme 4). The deuterium experiment revealed the formation
of triphenylvinylzirconocene 4a as intermediate.
Scheme 1: Transformation of alkynes to olefins.
On the other hand, carbozirconation of alkynes via reaction of
zirconacyclopentenes with alcohols, allyl ethers, homoallyl bro-
mides, vinyl ethers, alkynyl halides, and chloroformates gave
ethylzirconation [17], allylzirconation [18,19], cyclopropyl-
methylzirconation [20], vinylzirconation [21], alkynylzircona-
tion [22], and zirconoestification [23] products of alkynes, res-
pectively. However, to the best of our knowledge, this method
failed to fulfill arylzirconation of alkynes (Scheme 2).
Under similar reaction conditions, a study on the substrate
Recently, we have reported a p-chloranil (TCQ)-promoted scope was carried out, and the results are summarized in
reductive elimination reaction of the zirconate complex Table 1. When diphenylacetylene was used as starting material,
Li[Cp2Zr(C≡CR)3] toward geminal enediynes [44]. As part of different aryllithium compounds were employed to afford
our ongoing project on organozirconate chemistry [45-48], we triarylethylene in 38% to 62% isolated yields after being
envisioned that the use of an aryl ligand instead of one of the quenched with HCl (Table 1, entries 1–4). Bromination of the
alkynyl ligands would provide an arylzirconation product of the reaction mixture by NBS instead hydrolysis afforded bromo-
Scheme 2: Carbozirconation of alkynes via zirconacyclopentenes.
Scheme 3: TCQ-promoted reductive elimination of arylzirconate.
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Beilstein J. Org. Chem. 2014, 10, 528–534.
Scheme 4: TCQ-promoted arylzirconation of diphenylacetylene.
triphenylethylene in 37% isolated yield (Table 1, entry 5). tetraarylethylene in 31% yield (Table 1, entry 8). When other
When allyl bromide was employed as electrophile in the pres- diarylacetylene was employed in this reaction, the corres-
ence of CuCl, the allyltriarylethylenes were formed in 43% to ponding products were formed in 36% to 59% yields (Table 1,
45% yields (Table 1, entries 6 and 7). Cross coupling with entries 9–12). No desired product was observed when alky-
iodobenzene in the presence of CuCl/Pd(PPh3)4 afforded lacetylenes were used.
Table 1: Formation of multi-substituted olefins via the reaction of alkynes with [Cp2Zr(1-butene)(DMAP)] and aryllithium in the presence of TCQa.
entry
1
alkynes
aryllithium
PhLi
electrophiles
HCl
products
yield (%)b
62
3a
3b
3c
2
3
4
5
6
7
TolLi
2-ThLi
NaphLi
PhLi
HCl
HCl
58
47
38
37
45
43
HCl
3d
3e
3f
NBS
PhLi
allyl-Br
allyl-Br
TolLi
3g
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Beilstein J. Org. Chem. 2014, 10, 528–534.
Table 1: Formation of multi-substituted olefins via the reaction of alkynes with [Cp2Zr(1-butene)(DMAP)] and aryllithium in the presence of TCQa.
(continued)
8
TolLi
PhLi
PhLi
PhLi
PhLi
PhI
HCl
NBS
HCl
HCl
31
57
36
59
52
3h
3i
9
10
11
12
3j
3k
3l
aReaction conditions: Alkyne (1 mmol), [Cp2Zr(1-butene)(DMAP)] (1 mmol), ArLi (2 mmol), TCQ (2 mmol), electrophile (2 mmol). Tol = p-tolyl, Th =
2-thienyl, Naph = 1-naphthyl. bIsolated yield.
Recently, oxidative dimerization of alkenylcopper was reported
to afford conjugated dienes and polyenes [44,50-57]. When
triphenylvinylzirconocene 4a was reacted in the presence of
CuCl and TCQ, the 1,1,2,3,4,4-hexaphenyl-1,3-butadiene (5)
was formed in 43% isolated yield (Scheme 5). It is noteworthy
that in this reaction two molecular alkynes and two aryllithium
Scheme 5: Oxidative dimerization of 4a.
compounds were coupled in one-pot in the presence of Cp2Zr
species to afford highly substituted 1,3-butadienes.
reductive elimination to afford vinylzirconocene(II) 6. Then
The pathway of the oxidation of zirconate 2 to vinylzir- intermediate 6 reacts with TCQ to form vinylzirconocene(IV) 4.
conocene 4 is not yet clear. A possible mechanism is proposed The intermediate 4 reacts with electrophiles to afford multi-
in Scheme 6. Coordination of TCQ to zirconium results in substituted olefin 3.
Scheme 6: Possible reaction mechanism.
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Beilstein J. Org. Chem. 2014, 10, 528–534.
Conclusion
2.45 (s, 3H), 7.06 (s 1H), 7.20–7.42 (m, 14H); 13C NMR (75
We have developed a novel method for the zirconoarylation of MHz, CDCl3, Me4Si) δ 21.4, 126.8, 127.6, 127.7, 128.2, 128.8,
alkynes through TCQ-promoted reductive elimination of 129.1, 129.7, 130.6, 137.5, 137.7, 140.7, 140.9, 142.8; GC–MS
arylzirconate. This reaction can afford multi-substituted olefins m/z: 270.
with stereoselectivity.
(E)-1,2-Diphenyl-1-(2-thienyl)ethene (3c): The reaction was
Experimental
performed using 2-thienyllithium instead of phenyllithium, and
General Comments. All manipulations were conducted in 3c was isolated in 47% yield. 1H NMR (300 MHz, CDCl3,
Schlenk tubes and under a nitrogen atmosphere with a slightly Me4Si) δ 6.69–6.71 (dd, JHH = 3.8, 1.1 Hz, 1H), 6.87–6.90 (m,
positive pressure. Unless otherwise noted, all starting materials 1H), 6.93–6.96 (m, 2H), 7.04–7.09 (m, 4H), 7.13–7.15 (dd, JHH
were commercially available and were used without further = 4.8, 2.9 Hz, 1H), 7.26–7.36 (m, 5H); 13C NMR (75 MHz,
purification. Tetrahydrofuran (THF) was refluxed and freshly CDCl3, Me4Si) δ 124.8, 126.2, 126.4, 126.9, 127.5, 127.9,
distilled from dark purple solutions of sodium and benzophe- 128.1, 128.9, 129.5, 130.0, 136.3, 136.7, 139.5, 148.0; GC–MS
none under nitrogen atmosphere. 1H NMR and 13C NMR m/z: 262; HRMS: calcd for C18H14S, 262.0816; found,
spectra were recorded on 300 MHz and 400 MHz NMR spec- 262.0813.
trometers with TMS as internal standard. GC–MS spectra were
recorded on a Hewlett Packard GC–MS system.
(E)-1-(1-Naphthyl)-1,2-diphenylethene (3d) [59]: The reaction
was performed using 1-naphthyllithium instead of phenyl-
lithium, and 3d was isolated in 38% yield. 1H NMR (300 MHz,
CDCl3, Me4Si) δ 6.85 (s, 1H), 7.23–8.17 (m, 17H); 13C NMR
Typical procedure for TCQ-promoted arylzir-
conation of alkynes
To a solution of Cp2ZrCl2 (1.2 mmol, 351 mg) in 5 mL THF, (75 MHz, CDCl3, Me4Si) δ 125.4, 125.8, 126.1, 126.3, 127.1,
n-BuLi (2.4 mmol, 1.5 mL, 1.6 M in hexane) was added at 127.4, 127.5, 128.0, 128.2, 128.4, 128.5, 129.6, 129.9, 131.8,
−78 °C and the mixture was stirred for 1 h at the same tempera- 132.0, 134.1, 137.5, 141.1, 141.4, 142.3; GC–MS m/z: 306.
ture. To this solution, 4-dimethylaminopyridine (DMAP,
122 mg, 1.0 mmol) was added. The resulting mixture was 1-Bromo-1,2,2-triphenylethene (3e) [60]: The reaction mixture
warmed to room temperature and stirred for 1 h. Diphenylacety- containing 4a was further treated with NBS (2 mmol) for 4 h at
lene (1.0 mmol, 178 mg) was added and the mixture was stirred room temperature and 3e was isolated in 37% yield. 1H NMR
for 1 h at the same temperature. Subsequently, PhLi (2.0 mmol) (300 MHz, CDCl3, Me4Si) δ 6.93–6.97 (m, 3H), 7.02–7.05 (m,
was added and the solution was stirred for 12 h at room 3H), 7.11–7.17 (m, 3H), 7.27–7.33 (m, 3H), 7.35–7.37 (m, 3H);
temperature. Then TCQ (2.0 mmol) was added and stirred for 13C NMR (75 MHz, CDCl3, Me4Si) δ 122.3, 127.1, 127.7,
another 12 h to afford alkenylzirconocene 4a. The mixture was 128.0, 128.1, 128.2, 128.4, 129.7, 130.4, 130.4, 141.1, 141.2,
quenched with HCl solution to afford product 3a in 62% 143.7, 143.9; GC–MS m/z: 334, 336.
isolated yield.
1,1,2-Triphenylpenta-1,4-diene (3f) [27]: To the reaction mix-
1,1,2-Triphenylethene (3a) [58]: 1H NMR (300 MHz, CDCl3, ture containing 4a, CuCl (1 mmol) and allyl bromide (2 mmol)
Me4Si) δ 6.93 (s, 1H), 6.99–7.30 (m, 15H); 13C NMR (75 MHz, were added. The reaction mixture was stirred for 12 h at room
CDCl3, Me4Si) δ 126.6, 126.8, 127.5, 127.6, 127.7, 128.1, temperature and 3f was isolated in 45% yield. 1H NMR
128.3, 128.7, 129.7, 130.5, 137.5, 140.5, 142.7, 143.5; GC–MS (300 MHz, CDCl3, Me4Si) δ 3.28–3.30 (d, JHH = 6.1 Hz, 2H),
m/z: 256.
4.97–5.05 (m, 2H), 5.73–5.79 (m, 1H), 6.91–7.40 (m, 15H);
13C NMR (75 MHz, CDCl3, Me4Si) δ 40.6, 116.1, 126.2, 126.5,
2-Deuterium-1,1,2-triphenylethene (3a-D) [59]: The reaction 127.1, 127.6, 127.7, 128.0, 128.3, 129.8, 130.0, 131.0, 136.5,
mixture containing 4a was quenched with DCl, and 3a-D was 138.0, 140.9, 142.4, 143.1, 143.4; GC–MS m/z: 296.
isolated in 60% yield. 1H NMR (300 MHz, CDCl3, Me4Si) δ
7.00–7.51 (m, 15H); 13C NMR (75 MHz, CDCl3, Me4Si) δ (E)-1,2-Diphenyl-1-(p-tolyl)penta-1,4-diene (3g): The reaction
127.0, 127.6, 127.7, 127.7 (t, JDC = 7.2 Hz), 127.8, 128.2, was performed using p-tolyllithium instead of phenyllithium.
128.4, 128.8, 129.7, 130.6, 137.5, 140.5, 142.7, 143.6; GC–MS After treatment with TCQ for 12 h, CuCl (1 mmol) and allyl
m/z: 257.
bromide (2 mmol) was added. The reaction mixture was stirred
for 12 h at room temperature and 3g was isolated in 43% yield.
1,2-Diphenyl-1-(p-tolyl)ethene (3b) [58]: The reaction was 1H NMR (300 MHz, CDCl3, Me4Si) δ 2.44 (s, 3H), 3.36–3.38
using p-tolyllithium instead of phenyllithium, and 3b was (d, JHH = 6.1 Hz, 2H), 5.80–5.89 (m, 2H), 7.01–7.25 (m, 14H);
isolated in 58% yield. 1H NMR (300 MHz, CDCl3, Me4Si) δ 13C NMR (75 MHz, CDCl3, Me4Si) δ 21.4, 40.6, 116.0, 126.1,
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Beilstein J. Org. Chem. 2014, 10, 528–534.
126.3, 127.6, 128.0, 128.9, 129.7, 130.0, 131.0, 136.6, 136.6, 55.2, 55.3, 113.5, 114.2, 127.3, 127.5, 127.6, 128.2, 130.4,
137.7, 140.5, 140.8, 142.5, 143.3; GC–MS m/z: 310; HRMS: 130.9, 131.7, 132.9, 140.4, 144.1, 158.4, 158.9.
calcd for C24H22, 310.1722; found, 310.1724.
1,1,2,3,4,4-Hexaphenyl-1,3-butadiene (5) [62]: To the reaction
1,2,2-Triphenyl-1-(p-tolyl)ethene (3h) [61]: The reaction was mixture containing 4a, CuCl (1 mmol) and TCQ (2 mmol) were
performed using p-tolyllithium instead of phenyllithium. added. The reaction mixture was stirred for 12 h at room
To the reaction mixture, CuCl (1 mmol), Pd(PPh3)4 (0.05 temperature and compound 5 was isolated in 43% yield.
mmol), and iodobenzene (2 mmol) were added. The reaction 1H NMR (300 MHz, CDCl3, Me4Si) δ 6.96–7.40 (m, 30H);
mixture was stirred for 12 h at room temperature and 13C NMR (75 MHz, CDCl3, Me4Si) δ 127.1, 127.6, 128.0,
3h was isolated in 31% yield. 1H NMR (300 MHz, CDCl3, 128.0, 128.1, 128.2, 139.5, 140.4, 141.1, 142.0.
Me4Si) δ 2.28 (s, 3H), 3.94–7.12 (m, 19H); 13C NMR (75 MHz,
CDCl3, Me4Si) δ 21.3, 126.4, 126.4, 127.7, 127.8, 128.5, 131.3, Acknowledgements
131.4, 131.5, 136.1 ,140.6, 140.9 ,141.0, 144.1; GC–MS m/z: This work was supported by the National Key Basic Research
346.
Program of China (973 program) (2012CB933402) and
National Natural Science Foundation of China (21032004 and
(Z)-1-Phenyl-1,2-di(p-tolyl)ethene (3i) [58]: The reaction was 21272132). We also thank Ms. Yuanyuan Liu and Mr. Yudong
performed using ditolylacetylene instead of diphenylacetylene, He for their kind assistance in this work.
and 3i was isolated in 57% yield. 1H NMR (300 MHz, CDCl3,
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