Reactivity of alkynylzirconate toward α,β-unsaturated carbonyl compounds

Article abstract of DOI:10.1021/om301176e

The reaction of alkynylzirconates with α,β-unsaturated carbonyl compounds has been achieved. Reactions of alkynylzirconates with cinnamates afford ester-functionalized multisubstituted dienes, in which the C3 attacks cinnamates via Michael addition. Reactions of alkynylzirconates with benzylideneacetone give (1E,3Z)-dienes, in which benzylideneacetone acts as an electrophile to afford a proton.

Full text of DOI:10.1021/om301176e

Article
pubs.acs.org/Organometallics
Reactivity of Alkynylzirconate toward α,β-Unsaturated Carbonyl
Compounds
Xiaoyu Yan,† Yiqing Zhou,† and Chanjuan Xi*,†,‡
†Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education), Department of Chemistry,
Tsinghua University, Beijing 100084, People’s Republic of China
‡State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, People’s Republic of China
S
* Supporting Information
ABSTRACT: The reaction of alkynylzirconates with α,β-
unsaturated carbonyl compounds has been achieved. Reactions
of alkynylzirconates with cinnamates afford ester-functionalized
multisubstituted dienes, in which the C3 attacks cinnamates via
Michael addition. Reactions of alkynylzirconates with benzyli-
deneacetone give (1E,3Z)-dienes, in which benzylideneacetone
acts as an electrophile to afford a proton.
functionalized multisubstituted dienes 5,9 in which the C3
INTRODUCTION
■
attacked cinnamates via Michael addition. Reactions of
Organozirconocene complexes have attracted considerable
alkynylzirconates with benzylideneacetone gave (1E,3Z)-dienes
attention due to their fascinating structural features, their
6, in which benzylideneacetone acted as an electrophile to
unique Zr−C bonding, and their unusual capacity to induce
afford a proton (Scheme 1).
highly selective transformation reactions.1,2 One of the most
extensively studied areas is the chemistry of 16-electron
organozirconocene complexes, which has been widely explored,
RESULT AND DISCUSSION
■
Initially, to a THF solution of zirconate 1a, generated by the
and a tremendous number of applications in synthetic
n
reaction of BuLi with bis(phenylethynyl)zirconocene at room
chemistry have been found.1a−f,2 However, 18-electron organo-
temperature,6d was added 1 equiv of methyl cinnamate 7a
zirconate complexes, which have two cyclopentadienyl ligands,
three Zr−C bonds, and alkali-metal counterions, have been
Scheme 1. Diverse Reactivities of Alkynylzirconate with
postulated as key intermediates in a number of reactions.1g,3−6
Electrophiles
Thus, organozirconate complexes have been spectroscopically
identified in a novel class of carbon−carbon bond-forming
reactions.4,5 Negishi and co-workers found that organozirconate
complexes with three alkynyl groups show a dramatic 1,2-
migration insertion of Zr−C bond toward one of the CC
bonds to form enynes.6a−c Whitby and co-workers have
developed this reaction to various zirconate complexes to
afford many useful organic compounds via intramolecular
insertion reaction of organozirconates.4d,e,i,6d,e However,
intermolecular reactions of organozirconates were rarely
reported.7 Recently, our group reported that alkynylzirconates
1 showed a diverse reactivity with various electrophiles.8 When
aldehydes were used as electrophiles, dienols 2 were formed, in
which C4 attacked aldehydes.8a Carboxylic acid derivatives such
as chloroformate and ester were employed as electrophiles, and
functionalized allenes 3 were formed, in which C1 attacked the
carboxylic acid derivative.8a On the other hand, allyl bromide
was used as a electrophile and dienes 4 were obtained, in which
C3 attacked allyl bromide.8c As an ongoing study on the
alkynylzirconate chemistry, herein we wish to report the
reactivity of alkynylzirconates toward α,β-unsaturated carbonyl
compounds, which have both carbonyl and double bonds.
Reactions of alkynylzirconates with cinnamates afforded ester-
Received: December 4, 2012
Published: January 31, 2013
© 2013 American Chemical Society
869
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Organometallics
Article
(Scheme 2). The reaction mixture was stirred at 0 °C for 3 h
and quenched with a HCl solution; the 1,3-diene 5a was
unsaturated carbonyl compounds coordinates to zirconate 1
and induces coupling of alkynyl and zirconacyclopropene
species to give intermediate 10,10 which is in equilibrium with
11, 12, or 13. When cinnamate is used as the substrate, C3
attacks cinnamate via Michael addition11 to afford the
zirconacyclopentadiene 14.12 Hydrolysis of 14 over a short
time affords zirconium enolate 15 due to easy hydrolysis of the
two active Zr−C bonds. Further hydrolysis of 15 affords the
final product 5. The stepwise hydrolysis of 14 results in
controllable formation of trideuterated and dideuterated
products, respectively. The reactivity of zirconate toward
cinnamate is different with simple carbonyl complexes, such
as aldehyde, chloroformate, and ester8a but similar to that with
allyl bromide.8c When benzylideneacetone is used as the
substrate, C1 attacks the hydrogen of the methyl group with
triple-bond coordination to zirconium to afford 16. This may
be ascribed to the strong acidity of benzylideneacetone.
Hydrolysis of 16 affords the final product 6.
Scheme 2. Reaction of Alkynylzirconates with Methyl
Cinnamate
In summary, we have demonstrated the reactivity of
alkynylzirconate complexes toward α,β-unsaturated com-
pounds. Reactions of alkynylzirconate complexes with
cinnamates afforded ester-functionalized multisubstituted di-
enes, in which C3 attacked cinnamates via Michael addition.
Reactions of alkynylzirconates with benzylideneacetone
afforded (1E,3Z)-dienes. Further investigations on the reactivity
of alknylzirconates are now in progress.
formed and isolated in 36% yield. Increasing the amount of
methyl cinnamate to 2 equiv afforded 5a in 48% yield. The
yield did not significantly change when 3 equiv of 7a was
added. Deuteriolysis of the reaction mixture (within 12 h)
instead of hydrolysis afforded the trideuterated product 8a in
44% yield with >94% of deuterium incorporation. When the
reaction mixture was treated with DCl solution over 0.5 h,
dideuterated product 9a was formed in 47% yield with >95% of
deuterium incorporation. This result revealed that the
zirconium enolate skeleton existed before hydrolysis.
EXPERIMENTAL SECTION
■
General Comments. All manipulations were conducted in
predried Schlenk tube and under nitrogen with a slightly positive
pressure. Unless otherwise noted, all starting materials were used
without further purification. Tetrahydrofuran (THF) was refluxed and
freshly distilled from dark purple solutions of sodium and
benzophenone under a nitrogen atmosphere. 1H NMR and 13C
NMR spectra were recorded on a JEOL 300 NMR spectrometer with
TMS as internal standard. Flash column chromatography was
performed using silica gel (200−300 mesh). Elemental analyses were
performed on a Flash EA 1112 instrument.
A variety of cinnamates and zirconates were subjected to this
reaction. The representative results are summarized in Table 1.
Reaction of zirconate 1a with a variety of cinnamates 7 afforded
the corresponding 1,3-diene derivatives 5 in 43−50% isolated
yields (Table 1, entries 1−4). The structure of product 5b was
confirmed by 1H NMR, 13C NMR, HMQC, HMBC, and
NOESY. When acrylates or crotonates were employed, the
desired product did not form. When other zirconates were
employed, the corresponding 1,3-diene derivatives 5 also
formed in 37−54% isolated yields (Table 1, entries 5−8).
Next, alkynylzirconate 1a was treated with 1 equiv of
benzylideneacetone at 0 °C for 3 h. (1E,3Z)-1,4-Diphenyl-2-
butyl-1,3-butadiene (6) was formed in 53% isolated yield and
benzylideneacetone was recovered in 74% yield after workup
with HCl solution. Adding 2 equiv of benzylideneacetone did
not increase the yield of 6. When the reaction mixture was
quenched with DCl solution, 3,4-dideuterated 6-D was formed
in 50% isolated yield with >95% of deuterium incorportation
(Scheme 3). In this reaction, benzylideneacetone induced the
coupling reaction of alkynylzirconate and only one proton
joined in the product. It is noteworthy that no 6 was formed
when traditional protic reagents such as water, alcohol, acid and
primary amine were employed. In addition, when other
unsaturated ketones such as but-3-en-2-one, cyclohex-2-
enone, 1-cyclohexenylethanone, and acetophenone were used
in this reaction, the reactions did not proceed.
Representative Procedure for Coupling of Zirconate
Complexes with Ethyl Cinnamate. nBuLi (3.0 mmol, 1.6 M
solution in hexane) was added to a THF solution of phenylacetylene
(2.0 mmol) at −78 °C and stirred for 1 h. Then Cp2ZrCl2 (1.0 mmol)
was added. The solution was stirred at −78 °C for 1 h and then
another 12 h at room temperature. After the reaction mixture was
cooled to 0 °C, methyl cinnamate (2.0 mmol) was added and stirred
for 3 h. The reaction mixture was quenched with 2 N HCl for 12 h and
extracted with ethyl ether. The organic extract was dried over Na2SO4.
Removal of the solvent and subsequent purification by column
chromatography on silica gel (petroleum ether/EtOAc 50/1) afforded
1
5a (204 mg, 48%) as a colorless oil: H NMR (300 MHz, CDCl3,
3
Me4Si) δ 0.74 (t, JHH = 7.2 Hz, 3H), 0.87−1.35 (m, 4H), 1.72−1.82
(m, 1H), 2.26−2.35 (m, 1H), 2.95 (dd, J = 15.7, 7.8 Hz, 1H), 3.13
(dd, J = 15.7, 7.6 Hz, 1H), 3.66 (s, 3H), 5.05 (t, J = 7.7 Hz, 1H), 6.34
(s, 1H), 6.74 (s, 1H), 7.07−7.62 (m, 15H); 13C NMR (75 MHz,
CDCl3, Me4Si) δ 13.9, 22.7, 30.1, 30.9, 37.0, 39.9, 51.8, 126.4, 126.5,
127.0, 127.2, 128.2, 128.4, 128.6, 128.8, 129.0, 130.0, 130.2, 137.8,
138.0, 141.9, 144.3, 145.4, 172.8; HRMS calcd for C30H32O2 424.2402,
found 424.2408. Anal. Calcd for C30H32O2: C, 84.87; H, 7.60. Found:
C, 84.81; H, 7.68.
1
5b: colorless oil, 50% yield; H NMR (600 MHz, CDCl3, Me4Si) δ
3
0.72 (t, JHH = 7.3 Hz, 3H), 0.85−1.13 (m, 2H), 1.18 (t, J = 7.0 Hz,
3H), 1.23−1.27 (m, 2H), 1.72−1.77 (m, 1H), 2.29−2.34 (m, 1H),
2.91 (dd, J = 15.6, 7.6 Hz, 1H), 3.10 (dd, J = 15.6, 7.8 Hz, 1H), 4.10
(q, J = 7.1 Hz, 2H), 5.04 (t, J = 7.6 Hz, 1H), 6.32 (s, 1H), 6.71 (s,
1H), 7.11−7.56 (m, 15H); 13C NMR (150 MHz, CDCl3, Me4Si) δ
13.9, 14.3, 22.7, 30.1, 30.9, 37.3, 40.0, 60.6, 126.4, 126.5, 126.9, 127.3,
128.2, 128.3, 128.6, 128.8, 129.0, 130.0, 130.0, 137.8, 138.0, 141.9,
On the basis of the above results, a plausible mechanism was
proposed as follows (Scheme 4). First, the oxygen of α,β-
870
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Article
Table 1. Formation of Ester-Functionalized 1,3-Dienes 5 via the Reaction of Zirconates with Cinnamates
a
Isolated yield.
472.2169, found 472.2161. Anal. Calcd for C31H33ClO2: C, 78.71;
H, 7.03. Found: C, 78.78; H, 7.09.
Scheme 3. Reaction of Alkynylzirconate with
Benzylideneacetone
1
5d: colorless oil, 43% yield; H NMR (300 MHz, CDCl3, Me4Si) δ
3
0.74 (t, JHH = 7.2 Hz, 3H), 0.86−1.37 (m, 7H), 1.70−1.87 (m, 1H),
2.26−2.45 (m, 1H), 2.31 (s, 3H), 2.91 (dd, J = 15.7, 7.7 Hz, 1H), 3.09
(dd, J = 15.7, 7.6 Hz, 1H), 4.11 (q, J = 7.1 Hz, 2H), 5.02 (t, J = 7.6 Hz,
1H), 6.35 (s, 1H), 6.71 (s, 1H), 7.04−7.59 (m, 14H); 13C NMR (75
MHz, CDCl3, Me4Si) δ 13.9, 14.3, 21.0, 22.8, 30.1, 30.9, 37.4, 39.6,
60.6, 126.5, 126.9, 127.1, 128.2, 128.5, 128.9, 129.0, 129.9, 135.8,
137.9, 138.1, 138.8, 144.5, 145.7, 172.4; HRMS calcd for C32H36O2
452.2715, found 452.2717. Anal. Calcd for C32H36O2: C, 84.91; H,
8.02. Found: C, 84.85; H, 8.07.
144.4, 145.6, 172.3; HRMS calcd for C31H34O2 438.2559, found
438.2553. Anal. Calcd for C31H34O2: C, 84.89; H, 7.81. Found: C,
84.86; H, 7.88.
1
5e: colorless oil, 54% yield; H NMR (600 MHz, CDCl3, Me4Si) δ
3
1.15 (t, JHH = 7.1 Hz, 3H), 1.80 (s, 3H), 2.94 (dd, J = 15.3, 7.5 Hz,
1
5c: colorless oil, 47% yield; H NMR (300 MHz, CDCl3, Me4Si) δ
1H), 3.14 (dd, J = 15.3, 7.7 Hz, 1H), 4.04−4.11 (m, 2H), 5.03 (t, J =
7.6 Hz, 1H), 6.35 (s, 1H), 6.79 (s, 1H), 7.14−7.52 (m, 15H); 13C
NMR (150 MHz, CDCl3, Me4Si) δ 14.2, 19.1, 37.8, 40.4, 60.6, 126.4,
126.5, 126.9, 127.3, 128.2, 128.5, 128.5, 128.9, 129.2, 129.5, 130.0,
137.8, 138.1, 138.2, 142.2, 146.9, 172.3; HRMS calcd for C28H28O2
396.2089, found 396.2094. Anal. Calcd for C28H28O2: C, 84.81; H,
7.12. Found: C, 84.84; H, 7.16.
3
0.75 (t, JHH = 7.1 Hz, 3H), 0.81−1.32 (m, 7H), 1.75−1.82 (m, 1H),
2.26−2.35 (m, 1H), 2.89 (dd, J = 15.8, 7.2 Hz, 1H), 3.06 (dd, J = 15.8,
8.0 Hz, 1H), 4.10 (q, J = 7.1 Hz, 2H), 4.98 (t, J = 7.6 Hz, 1H), 6.30 (s,
1H), 6.71 (s, 1H), 7.10−7.50 (m, 15H); 13C NMR (75 MHz, CDCl3,
Me4Si) δ 13.9, 14.3, 22.8, 30.1, 30.9, 37.4, 39.7, 60.7, 126.6, 127.1,
128.3, 128.4, 128.7, 128.7, 128.8, 128.9, 130.2, 130.3, 132.2, 137.6,
137.9, 140.5, 143.9, 145.1, 172.0; HRMS calcd for C31H33ClO2
871
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Scheme 4. Plausible Mechanism of the Reaction with α,β-Unsaturated Carbonyl Compounds
1
5f: colorless oil, 48% yield. H NMR (300 MHz, CDCl3, Me4Si) δ
1.79 (s, 3H), 2.94 (dd, J = 15.6, 7.6 Hz, 1H), 3.13 (dd, J = 15.5, 7.6
Hz, 1H), 3.61 (s, 3H), 5.00 (t, J = 7.6 Hz, 1H), 6.33 (s, 1H), 6.78 (s,
1H), 7.15−7.46 (m, 15H); 13C NMR (75 MHz, CDCl3, Me4Si) δ 19.1,
37.5, 40.4, 51.8, 126.4, 126.5, 127.0, 127.2, 128.2, 128.5, 128.5, 128.9,
129.2, 129.6, 130.0, 137.7, 138.1, 138.2, 142.1, 146.8, 172.8; HRMS
calcd for C27H26O2 382.1933, found 382.1931. Anal. Calcd for
C27H26O2: C, 84.78; H, 6.85. Found: C, 84.82; H, 6.93.
129.0, 129.4 (t, J = 27.3 Hz), 129.8 (t, J = 24.4 Hz), 137.8, 138.0,
141.9, 144.1, 145.2, 172.8; HRMS calcd for C30H30D2O2 426.2528,
found 426.2524. Anal. Calcd for C30H30D2O2: C, 84.47; H, 8.03.
Found: C, 84.41; H, 8.01.
1
6: colorless oil, 53% yield; H NMR (300 MHz, CDCl3, Me4Si) δ
3
0.84 (t, JHH = 7.2 Hz, 3H), 1.23−1.31 (m, 2H), 1.45−1.53 (m, 2H),
2.35 (t, 3JHH = 7.9 Hz, 3H), 6.18 (d, J = 12.1 Hz, 1H), 6.44 (d, J = 12.1
Hz, 1H), 6.51 (s, 1H), 7.17−7.48 (m, 5H); 13C NMR (75 MHz,
CDCl3, Me4Si) δ 14.0, 23.0, 30.9, 31.1, 126.6, 127.0, 128.2, 128.3,
128.7, 129.0, 129.5, 129.7, 133.9, 137.8, 137.9, 139.8; HRMS calcd for
C20H22 262.1722, found 262.1728. Anal. Calcd for C20H22: C, 91.55;
H, 8.45. Found: C, 91.46; H, 8.40.
1
5g: colorless oil, 42% yield; H NMR (300 MHz, CDCl3, Me4Si) δ
0.82 (t, 3JHH = 7.2 Hz, 3H), 0.98−1.26 (m, 10H), 1.67−1.74 (m, 1H),
2.24−2.32 (m, 1H), 2.91 (dd, J = 15.8, 7.3 Hz, 1H), 3.09 (dd, J = 15.8,
7.6 Hz, 1H), 3.63 (s, 3H), 5.01 (t, J = 7.6 Hz, 1H), 6.31 (s, 1H), 6.70
(s, 1H), 7.12−7.50 (m, 15H); 13C NMR (75 MHz, CDCl3, Me4Si) δ
14.2, 22.7, 28.6, 29.3, 30.3, 31.6, 37.0, 39.8, 51.8, 126.4, 126.5, 127.0,
127.2, 128.2, 128.4, 128.6, 128.8, 129.0, 130.0, 130.1, 137.8, 138.0,
141.9, 144.4, 145.4, 172.8; HRMS calcd for C32H36O2 452.2715, found
452.2711. Anal. Calcd for C32H36O2: C, 84.91; H, 8.02. Found: C,
84.87; H, 8.06.
6-D: colorless oil, 53% yield; 1H NMR (300 MHz, CDCl3, Me4Si) δ
3
0.83 (t, JHH = 7.2 Hz, 3H), 1.24−1.32 (m, 2H), 1.45−1.53 (m, 2H),
3
2.33 (t, JHH = 7.8 Hz, 3H), 6.52 (s, 1H), 7.16 − 7.47 (m, 5H); 13C
NMR (75 MHz, CDCl3, Me4Si) δ 14.0, 23.0, 30.9, 31.2, 126.6, 127.0,
3
128.2, 128.3, 128.7, 129.0, 129.5, 129.8 (t, JDC = 20.0 Hz), 133.4 (t,
3JDC = 24.5 Hz), 137.8, 138.0, 139.8; HRMS calcd for C20H20D2
264.1847, found 264.1844. Anal. Calcd for C20H20D2: C, 90.85; H,
9.15. Found: C, 90.81; H, 9.13.
1
5h: colorless oil, 37% yield; H NMR (300 MHz, CDCl3, Me4Si) δ
3
0.71 (t, JHH = 7.2 Hz, 3H), 0.88−1.30 (m, 4H), 1.68−1.77 (m, 1H),
2.25−2.36 (m, 7H), 2.89 (dd, J = 15.8, 7.6 Hz, 1H), 3.13 (dd, J = 15.8,
7.6 Hz, 1H), 3.62 (s, 3H), 5.01 (t, J = 7.6 Hz, 1H), 6.25 (s, 1H), 6.65
(s, 1H), 7.02 − 7.52 (m, 13H); 13C NMR (75 MHz, CDCl3, Me4Si) δ
13.9, 21.3, 21.3, 22.8, 30.1, 30.9, 37.1, 40.0, 51.8, 126.3, 127.3, 128.3,
128.8, 128.9, 129.0, 129.3, 129.8, 130.0, 134.5, 135.0, 135.2, 136.1,
136.6, 142.0, 143.8, 172.8; HRMS calcd for C32H36O2 452.2715, found
452.2721. Anal. Calcd for C32H36O2: C, 84.91; H, 8.02. Found: C,
84.84; H, 8.08.
ASSOCIATED CONTENT
■
S
* Supporting Information
Figures giving HMQC, HMBC, and NOESY spectra of
compounds 5b,e. This material is available free of charge via
the Internet at http://pubs.acs.org.
1
8a: colorless oil, 44% yield; two stereoisomers with dr = 2:1; H
NMR (300 MHz, CDCl3, Me4Si) δ 0.72 (t, 3JHH = 7.2 Hz, 3H), 0.88−
1.32 (m, 3H), 1.70−1.80 (m, 1H), 2.29−2.39 (m, 2H), 2.88−3.08 (m,
1H in 2:1 ratio), 3.62 (s, 3H), 5.01 (d, J = 7.6 Hz, 1H), 7.10 − 7.61
(m, 15H); 13C NMR (75 MHz, CDCl3, Me4Si) δ 13.9, 22.7, 30.0, 30.9,
37.0(m, C-D), 39.8, 51.8, 126.4, 126.5, 127.0, 127.2, 128.3, 128.4,
128.6, 128.8, 129.0, 130.0−130.2 (m, C-D), 137.8, 137.9, 141.9, 144.1,
145.2, 172.8; HRMS calcd for C30H29D3O2 427.2591, found 427.2594.
Anal. Calcd for C30H29D3O2: C, 84.27; H, 8.25. Found: C, 84.22; H,
8.20.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: cjxi@tsinghua.edu.cn.
Notes
The authors declare no competing financial interest.
1
9a: colorless oil, 47% yield; H NMR (300 MHz, CDCl3, Me4Si) δ
ACKNOWLEDGMENTS
■
3
0.72 (t, JHH = 7.2 Hz, 3H), 0.88−1.29 (m, 4H), 1.73−1.77 (m, 1H),
This work has been supported by the National Natural Science
Foundation of China (Nos. 20972085, 21032004, and
21272132), and the National Key Basic Research Program of
China (973 program) (No. 2012CB933402).
2.30−2.34 (m, 1H), 2.93 (dd, J = 15.7, 7.8 Hz, 1H), 3.10 (dd, J = 15.7,
7.5 Hz, 1H), 3.64 (s, 3H), 5.03 (t, J = 7.6 Hz, 1H), 7.07 − 7.58 (m,
15H); 13C NMR (75 MHz, CDCl3, Me4Si) δ 13.9, 22.8, 30.0, 30.9,
37.1, 39.9, 51.8, 126.4, 126.5, 127.0, 127.2, 128.2, 128.4, 128.6, 128.8,
872
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dx.doi.org/10.1021/om301176e | Organometallics 2013, 32, 869−873