Ru(II)-Catalyzed Cross-Coupling of Cyclopropenes with Diazo Compounds: Formation of Olefins from Two Different Carbene Precursors

Article abstract of DOI:10.1021/acs.joc.7b02634

Formal carbene dimerization is a convergent method for the synthesis of alkenes. Herein, we report a Ru(II)-catalyzed carbene dimerization of cyclopropenes and diazo compounds. The yields are up to 97% and the stereoselectivity are up to >20:1. Mechanistically, it has been experimentally demonstrated that the catalyst reacts with cyclopropene first to generate a Ru(II)-carbene species, which is attacked by nucleophilic diazo substrate, followed by dinitrogen extrusion to form the double bond.

Full text of DOI:10.1021/acs.joc.7b02634

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Note
Ru(II)-Catalyzed Cross-Coupling of Cyclopropenes with Diazo
Compounds: Formation of Olefins from two Different Carbene Precursors
Bo Wang, Heng Yi, Hang Zhang, Tong Sun, Yan Zhang, and Jianbo Wang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b02634 • Publication Date (Web): 18 Dec 2017
Downloaded from http://pubs.acs.org on December 18, 2017
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The Journal of Organic Chemistry
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Ru(II)-Catalyzed Cross-Coupling of Cyclopropenes with Diazo
Compounds: Formation of Olefins from two Different Carbene
Precursors
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Bo Wang,†,§ Heng Yi,†,§ Hang Zhang,† Tong Sun,† Yan Zhang† and Jianbo Wang*,†,‡
†Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic
Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking
University, Beijing 100871, China; ‡The State Key Laboratory of Organometallic Chemistry, Chinese
Academy of Sciences, Shanghai 200032, China
RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required
according to the journal that you are submitting your paper to)
ABSTRACT. Formal carbene dimerization is a convergent method for the synthesis of alkenes. Herein
we report a Ru(II)-catalyzed carbene dimerization of cyclopropenes and diazo compounds. The yields
are up to 97% and the stereoselectivity are up to >20:1. Mechanistically, it has been demonstrated by
experiments that the catalyst reacts with cyclopropene first to generate a Ru(II)-carbene species, which is
attacked by nucleophilic diazo substrate, followed by dinitrogen extrusion to form the double bond.
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Bearing a resemblance to Wittig reaction and olefin metathesis, formal carbene dimerization is an
alternative method for the synthesis of alkenes. However, suffering from the competing homo-coupling
and poor stereoselectivity of the formed double bond, this transformation has not found widespread
applications. One way to overcome the above-mentioned problems is to carry out the reaction in
intramolecular manner (Scheme 1, a).1 For example, the groups of Doyle1c and Che1d have achieved
Rh(II)- and Ru(II)-catalyzed reactions of bis(diazocarbonyl) compounds to construct cycloalkenes. Some
other examples of Rh(II)- and Au(I)-catalyzed cyclization of bis-N-tosylhydrazones have been recently
reported by the groups of Wang1e and Sun.1g
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However, in terms of synthetic applications, chemo- and stereoselective intermolecular formal
carbene dimerization reactions of two different diazo substrates are obviously desirable but are also
more challenging.2 To achieve such goal, fine-tuning the reactivity of two different diazo substrates is
necessary. In this regard, the groups of Davies2b and Sun2c,d have made significant progress (Scheme 1,
b).
Recently a new strategy to achieve formal carbene dimerization has emerged.3 In this strategy, a
nucleophilic diazo substrate is set to react with a non-diazo carbene precursor (Scheme 1, c). In 2001,
Barluenga and co-workers achieved the reaction of Cu(I)-catalyzed diazo compounds with Fischer
carbene complex.3b We have subsequently reported a catalyst-free reaction of diazo compounds with
Fischer carbene complexes.3c Moreover, we have also developed a catalyst-free synthesis of 1,1-
difluoroolefins through formal carbene dimerization between difluorocarbene and diazo compounds.3d
Other examples along this line include the cross-coupling reactions of diazo compounds with
propargylic esters, as developed by the groups of Barluenga4a, Dixneuf4b, Burneau and Dérien.4c These
reports indicate that the controlling of the chemo- and stereoselectivity are possible following the above
strategy, while the major limitation is that the non-diazo substrates are still rather limited. Thus, it is
highly desirable to search for other non-diazo substrates for the formal carbene dimerization.
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Scheme 1. Strategy for Chemo-Selective Carbene Dimerization
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Cyclopropene shows diverse reactivity because of the high strain of the small ring, which makes
this type of unique compound excellent three-carbon building blocks in organic synthesis.5 Among the
various transformations, transition-metal-catalyzed generation of vinyl metal carbene has attracted
considerable attentions in recent years.5b-e The metal carbene species generated from cyclopropenes
undergo typical carbene transformations, such as C-H bond insertions,6 O-H bond insertions7 and
cyclopropanations.8 As the continuation of our interest in the exploration of cyclopropenes as vinyl
metal carbene precursors,9 we have conceived that it may be possible to use cyclopropene as a source for
metal carbene in the formal carbene dimerization. Herein we reported the Ru(II)-catalyzed carbene
dimerization of cyclopropenes and diazo compounds.10
At the outset of this study, we employed 3,3-dihexylcycloprop-1-ene 1a and methyl 2-diazo-2-
phenylacetate 2a as the model substrate to optimize the reaction conditions. Firstly, we tested various
transition-metal catalysts, which could react with cyclopropene to generate vinyl metal carbenes. A
series of transition-metal catalysts, including CuI, AuCl, AuPPh3Cl, [Rh(cod)Cl]2, and [RuCl2(p-
cymene)]2were examined (Table 1, entries 1-5). [RuCl2(p-cymene)]2 showed the highest efficiency
among these catalysts (entry 5). Consequently, we proceeded to further examine other Ru(II) catalysts
(entries 6-9), and it was found that [Cp*Ru(cod)Cl] (Cp* = C5Me5) afforded the optimal result (entry 9).
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Furthermore, changing the solvent from toluene to THF and slightly increasing the amount of
cyclopropene 1a could further improve the yield. Under the optimized conditions, 3a could be isolated
in 88% yield with E:Z of 5:1 (Table 1). At last, control experiment was carried out in the absence of the
catalyst. No reaction occurred under such conditions (entry 11).
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Table 1. Optimization of the Reaction Conditions
entry solvent
1a:2a
1:1
cat.
CuI
yield (%)a E/Zb
1
2
MeCN
MeCN
MeCN
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
THF
10
19
ndc
nd
1:1
AuCl
3d
4
1:1
AuPPh3Cl
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nd
1:1
[Rh(cod)Cl]2
[RuCl2(p-cymene)]2
Ru(PPh3)3Cl2
CpRu(PPh3)2Cl
[RuCl2(benzene)]2
[Cp*Ru(cod)Cl]
[Cp*Ru(cod)Cl]
none
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nd
5
1:1
43
3:1
4:1
10:1
2.5:1
3:1
5:1
--
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1:1
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7
1:1
21
8
1:1
37
9
1:1
72
10e
11g
1.3:1
1.3:1
98(88f)
0
THF
b
1
c
aNMR yield. Determined by H NMR (400 MHz). nd: not determined.
e
f
d5 mol% AgOTf was used. 2.5 mol% catalyst was used. Isolated yield.
gThe substrates remained unchanged.
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With the optimized reaction conditions, the scope of cyclopropenes was then examined. As
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illustrated in Scheme 2, various 3,3-disubstituted cyclopropenes reacted smoothly with methyl 2-diazo-
2-phenylacetate 2a to afford the corresponding products in moderate to good yields. However, the
stereoselectivity of these cyclopropenes were not satisfactory except the reaction with 3,3-diphenyl
cyclopropene. Isomers of the product (3d and 3d'), which bear an adamantly substituent, can be
separated by column chromatography, while all of the other products were inseparable mixtures. The
configurations of these two isomers were confirmed by NOESY spectra, confirming that the E,E isomer
is the major product. By comparing the products' NMR spectra, we assume that in all the cases the E
isomers are the major products.
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Scheme 2. Scope of the Cyclopropenesa
aReaction conditions: 1a-f (0.26 mmol), 2a (0.20 mmol), and [Cp*Ru(cod)Cl] (2.5 mol%) in THF (1.0
o
mL) at 60 C. All the yields refer to the isolated products by column chromatography. The ratio of E:Z
was determined by 1H NMR (400 MHz). bThe reaction time was 12 h and 1.5 equiv of cyclopropene was
used.
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Next, the scope of diazo substrates was examined with a series of diazo esters. As shown in Scheme
3, the substituents on the aromatic ring of the aryldiazoacetates did not significantly affect the reaction,
except that strong electron-withdrawing substituents reduce the yields (3l, m). The steric effects at ortho
position of the aromatic ring had a negative effect on the results. The substrate bearing a fluoro
substituent at the ortho position gave the corresponding product 3k in 58% yield, while the sterically
bulkier ortho chloro substituent completely shut down the reaction (3t). Moreover, the reaction with
diazo compounds bearing alkyl group also proceeded, affording the corresponding products in good
yields (3q, 3s). However, the stereoselectivity of the reaction was rather poor in these cases. Finally, the
reaction with diazo substrate bearing two ester groups also worked well to give product in 82% yield.
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Scheme 3. Scope of the Diazo Compounds
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aReaction conditions: 1a,c,d (0.26 mmol), 2b-n (0.20 mmol), and [Cp*Ru(cod)Cl] (2.5 mol%) in THF
o
(1.0 mL) at 60 C. All of the yields refer to the isolated products by column chromatography. The ratio
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b
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c
of E:Z was determined by H NMR. The reaction temperature was 70 C. 2.0 equiv of cyclopropene
d
o
e
was used. The reaction was carried in PhMe (1.0 mL) at 50 C. The yield was estimated by 1H NMR
f
(400 MHz). Reaction conditions: 1d (0.2 mmol), 2l (0.4 mmol) and [Cp*Ru(cod)Cl] (2.5 mol%) in
PhMe (0.4 mL) at 60 oC.
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We have proposed two possible reaction pathways for this formal carbene dimerization reaction
(Scheme 4, path a and path b). The major difference between these two pathways is which substrate,
cyclopropene or diazo compound, first reacts with the catalyst to generate the corresponding Ru(II)
carbene species.
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Scheme 4. Proposed Reaction Pathways
To gain insights into the reaction mechanism, in particular the differentiation of the two possible
pathways, some mechanistic experiments were carried out. First, pairwise competition experiments of
2a/2g and 2a/2b under the standard conditions were carried out. The ratios of the products clearly
demonstrate that the diazo compounds bearing electro-donating substituents on the aromatic ring are
more reactive (Scheme 5). The results imply that the diazo substrate likely functions as a nucleophile in
the reaction, which is in accordance with path b shown in Scheme 4.
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Scheme 5. Competition Experiments of the Diazo Compounds
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Subsequently, the starting materials, the diazo compound and the cyclopropene, were treated
separately under the standard conditions (Scheme 6). Both cyclopropene 1a and diazo compound 2a
could react under the Ru(II) catalysis, resulting in the formation of self-dimerization products 4 and 5 in
42% and 43% yield, respectively. The results suggest that the formation of Ru(II) carbene from
cyclopropene or diazo compound occurs at similar rate. However, the diazo compound bearing two ester
groups 2m remained unchanged under Ru(II)-catalysis. Thus, in case of Ru(II)-catalyzed reaction of 2m
and 1d to give 3r, it is unambiguous that cyclopropene 1d first reacts with Ru(II) catalyst to generate
vinyl Ru(II) carbene intermediate.
Scheme 6. Control Experiments
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While examining the scope of diazo compounds, it was found that diazo compounds bearing an
alkenyl group gave no products. It is thus suspected that the alkenyl moieties may hamper the reaction.
In order to confirm the effect of alkenyl moiety on the reaction, the Ru(II)-catalyzed reactions were
carried out in the presence of additional alkenes (Scheme 7). Cyclohexene was found to slow down the
reaction, while 1-dodecene completely shut down the reaction. The negative effect of alkene to the
cross-coupling reaction may be attributed to the relatively strong coordination effect of the alkene with
the Ru(II) catalyst, thus preventing the interaction of cyclopropene or diazo substrate with the catalyst.
Scheme 7. The Effect of Alkenyl Groups on the Reaction
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Based on the experimental observation, a plausible mechanism was proposed as depicted in Scheme
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8. Firstly, Ru(II) catalyst reacts with cyclopropene A to generate a coordination complex B. In the
presence of olefin, the olefin bonds to Cp*Ru(cod) to form relatively stable complex C, thus competing
the complexation with cyclopropene substrate. From complex B, ring opening of cyclopropene leads to
the formation of vinyl Ru(II) carbene intermediate D. Nucleophilic addition of diazo compound E to
Ru(II) carbene intermediate D generates the adduct F. Subsequently, dinitrogen extrusion affords the
final product G, with regeneration of the Ru(II) catalyst.
Scheme 8. Proposed Reaction Mechanism
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In summary, a new type of Ru(II) catalyzed carbene-dimerization of cyclopropenes and diazo
compounds has been developed. A series of cyclopropenes and diazo compounds were tolerated in this
formal carbene dimerization, and the corresponding 1,3-butadiene products could be obtained in
moderate to good yields. Notably, homo coupling products were not observed, suggesting the high
selectivity of the substrates toward Ru(II) catalysts. The results indicate that carbene-dimerization
between two different carbene precursors can be a general strategy for the construction of double bonds.
Finally, it is also a demonstration of novel application of the vinyl metal carbenes that are generated in
situ from cyclopropenes.
EXPERIMENTAL SECTION
General Methods. Air- and moisture-sensitive reactions were carried out in oven-dried glassware
sealed with rubber septa under nitrogen atmosphere. THF and PhMe were distilled from sodium with
benzophenone as indicator. [Cp*Ru(cod)Cl] and other metal salts were commercially available.
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Purification of products was accomplished by flash chromatography on silica gel (200-300 mesh, from
Qingdao, China) NMR spectra were measured on a Bruker ARX400 (1H at 400 MHz, 13C at 100 MHz)
magnetic resonance spectrometer. Chemical shifts are reported in ppm using tetramethylsilane as
internal standard (s = singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublets, m =
multiplet). IR spectra were recorded on a Nicolet Avatar 330 Fourier transform spectrometer (FT-IR)
and are reported in wave numbers (cm-1). For HRMS measurements, the mass analyzer is FT-ICR. PE:
petroleum ether; EA: ethyl acetate.
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The preparation of cyclopropenes. Cyclopropenes 1a, 1b, 1c, 1d, 1e and 1f were known and
prepared via literature procedures. 9d
General procedure for the Ru(II)-catalyzed reactions. A 10 mL oven-dried Schlenk flask was
charged with [Cp*Ru(cod)Cl] (1.9 mg, 0.005 mmol, 2.5 mol%) under nitrogen. Then dry THF (1.0 mL)
was added using a syringe. Cyclopropene (0.26 mmol, 1.3 equiv) and diazo compound (0.20 mmol, 1.0
equiv) were successively added by syringe. The reaction was heated at 60 oC while keeping stirring for 4
h, then reaction mixture was cooled to room temperature. The reaction mixture was filtered through a
short column of silica gel eluted by chloroform. The solvent was then removed in vacuo to leave a crude
mixture, which is purified by silica gel column chromatography to afford pure products.
The reaction of 2l and 2n were carried in PhMe (1.0 mL) at 50 oC. The reaction of 1d (0.20 mmol,
1.0 equiv) and 2m (0.40 mmol, 2,0 equiv) were carried out in PhMe (0.4 mL)
Methyl-5-hexyl-2-phenylundeca-2,4-dienoate (3a). A colorless oil; yield: 63.0 mg (88%); E:Z =
5:1; Rf = 0.55 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 12.0 Hz, 5.3H), 7.28-7.39 (m,
25.2H), 7.20-7.22 (m, 6.3H), 6.96 (d, J = 11.8 Hz, 1H), 6.63 (d, J = 11.8 Hz, 1H), 3.82 (s, 3H), 3.75 (s,
5.3H), 2.32 (t, J = 7.4 Hz, 10.6H), 2.26 (t, J = 7.5 Hz, 2H), 2.17 (t, J = 7.5 Hz, 2H), 2.03 (t, J = 7.4 Hz,
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10.6H), 1.20-1.46 (m, 118H), 0.84-0.92 (m, 42H); C NMR (100 MHz, CDCl3) δ 168.5, 155.3, 153.5,
138.8, 136.7, 135.5, 134.0, 130.3, 130.0, 129.6, 128.2, 127.8, 127.6, 127.38, 127.33, 121.5, 121.3, 52.0,
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38.2, 37.9, 31.7, 31.6, 31.6, 31.2, 29.4, 29.3, 29.2, 29.1, 29.0, 28.2, 27.9, 22.6, 14.11, 14.07; HRMS (EI,
m/z) calcd for C24H36O2 [M]+ 356.2710, found 356.2712; IR (film): 2955, 1713, 1623, 1461, 1433, 1242,
1194, 1139 cm-1.
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Methyl 5,5-dicyclohexyl-2-phenylpenta-2,4-dienoate (3b). A colorless oil; yield: 47.2 mg, (67%);
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E:Z = 8:1; Rf = 0.52 (PE:EA = 30:1); H NMR (400 MHz, CDCl3) δ 7.93 (d, J = 12.0 Hz, 7.6H), 7.30-
7.40 (m, 25.8H), 7.20-7.23 (m, 17.2H), 7.11 (d, J = 11.9 Hz, 1H), 6.70 (d, J = 12.0 Hz, 1H), 5.86 (d, J =
12.0 Hz, 7.6H), 3.82 (s, 3H), 3.76 (s, 22.8H), 2.68-2.85 (m, 8.6H), 1.97-2.08 (m, 8.6H), 0.90-1.80 (m,
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172H); C NMR (100 MHz, CDCl3) δ 168.6, 168.5, 164.5, 162.9, 139.1, 136.4, 135.4, 134.4, 130.4,
129.7, 129.5, 128.2, 127.7, 127.3, 119.3, 119.0, 52.0, 51.7, 41.7, 41.5, 41.2, 34.3, 33.9, 30.9, 29.7, 26.9,
26.7, 26.4, 26.3, 26.1, 26.0, 25.9; HRMS (EI, m/z) calcd for C24H32O2 [M]+ 352.2397, found 352.2397;
IR (film): 2957, 1706, 1629, 1466, 1254, 1175 cm-1.
Methyl (E)-2,5,5-triphenylpenta-2,4-dienoate (3c).11 A yellow solid (m.p. = 142-145 C); yield:
o
57.9 mg (85%); E:Z > 20:1; Rf = 0.38 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 11.8
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Hz, 1H), 7.31-7.46 (m, 7H), 7.14-7.27 (m, 8H), 6.67 (d, J = 11.8 Hz, 1H), 3.69 (s, 3H); C NMR (100
MHz, CDCl3) δ 168.1, 150.9, 141.6, 138.9, 138.1, 135.3, 133.2, 130.6, 130.4, 128.5, 128.3, 128.2, 128.2,
128.0, 127.7, 123.7, 52.1.
Methyl (2E,4E)-5-((3r,5r,7r)-adamantan-1-yl)-2-phenylhexa-2,4-dienoate (3d). A white solid
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(m.p. = 118-121 C); yield: 28.8 mg (43%); Rf = 0.46 (PE:EA = 20:1); H NMR (400 MHz, CDCl3) δ
7.84 (d, J = 11.8 Hz, 1H), 7.22-7.40 (m, 5H), 5.96 (d, J = 11.8 Hz, 1H), 3.75 (s, 3H), 1.92-1.96 (m, 6H),
1.57-1.70 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 168.5, 158.0, 137.6, 135.6, 130.3, 130.3, 127.9,
127.4, 118.4, 52.0, 40.4, 39.2, 36.8, 28.5, 13.2; HRMS (EI, m/z) calcd for C23H29O2 [M+H]+ 337.2162,
found 337.2156; IR (film): 2903, 1710, 1616, 1433, 1244, 1208 cm-1.
Methyl (2Z,4E)-5-((3r,5r,7r)-adamantan-1-yl)-2-phenylhexa-2,4-dienoate (3d’). A white solid
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1
(m.p. = 119-122 C); yield: 12.6 mg (19%); Rf = 0.49 (PE:EA = 20:1); H NMR (400 MHz, CDCl3) δ
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7.28-7.35 (m, 5H), 7.02 (d, J = 11.6 Hz, 1H), 6.75 (d, J = 11.6 Hz, 1H), 3.83 (s, 3H), 2.05 (s, 3H), 1.86
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(s, 3H), 1.66-1.74 (m, 12H); C NMR (100 MHz, CDCl3) δ 168.6, 156.3, 139.1, 135.5, 130.7, 128.2,
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127.8, 127.4, 118.8, 51.8, 40.6, 39.2, 36.9, 28.6, 12.6; HRMS (EI, m/z) calcd for C23H29O2 [M+H]+
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337.2162, found 337.2156; IR (film): 2905, 1712, 1617, 1449, 1433, 1202 cm-1.
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Methyl (E)-4-cyclooctylidene-2-phenylbut-2-enoate (3e). A colorless oil; yield: 33.0 mg (58%);
E:Z = 4:1; Rf = 0.51 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 12.1 Hz, 4.1H), 7.28-
7.40 (m, 15.3H), 7.20-7.23 (m, 10.2H), 6.98 (d, J = 12.0 Hz, 1H), 6.67 (d, J = 12.0 Hz, 1H), 5.90 (d, J =
12.1 Hz, 4.1H), 3.82 (s, 3H), 3.75 (s, 12.3H), 2.52 (t, J = 6.2 Hz, 8.2H), 2.45 (t, J = 6.2 Hz, 2H), 2.36 (t,
J = 5.9 Hz, 2H), 2.20 (t, J = 6.0 Hz, 8.2H), 1.62-1.80 (m, 20.4H), 1.46-1.52 (m, 30.6H); 13C NMR (100
MHz, CDCl3) δ 168.5, 157.8, 155.7, 138.9, 136.6, 135.6, 134.1, 130.4, 129.1, 128.2, 127.8, 127.6, 127.3,
127.3, 122.2, 121.8, 52.0, 51.7, 38.7, 38.4, 29.9, 29.7, 29.4, 28.7, 28.5, 27.6, 27.4, 26.3, 26.2, 25.8,
25.64, 25.60; HRMS (EI, m/z) calcd for C19H24O2 [M]+ 284.1771, found 284.1771; IR (film): 2927,
1710, 1615, 1433, 1242, 1201, 1136 cm-1.
Methyl (E)-4-cyclododecylidene-2-phenylbut-2-enoate (3f). A colorless oil; yield: 51.1 mg (75%);
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E:Z = 5:1; Rf = 0.50 (PE:EA = 30:1); H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 11.9 Hz, 5.0H), 7.28-
7.39 (m, 18.0H), 7.21-7.23 (m, 12.0H), 7.02 (d, J = 11.8 Hz, 1H), 6.76 (d, J = 11.7 Hz, 1H), 5.97 (d, J =
11.9 Hz, 5.0H), 3.81 (s, 3H), 3.76 (s, 15.0H), 2.39 (t, J = 6.7Hz, 10.0H), 2.32 (t, J = 6.7 Hz, 2H), 2.25 (t,
J = 6.7 Hz, 2H), 2.13 (t, J = 6.7 Hz, 10.0H), 1.21-1.69 (m, 108H); 13C NMR (100 MHz, CDCl3) δ 168.6,
168.5, 153.4, 151.5, 138.8, 136.8, 135.5, 134.2, 130.4, 130.0, 129.8, 128.2, 127.8, 127.6, 127.3, 122.5,
122.3, 52.0, 51.7, 32.9, 32.8, 30.0, 29.4, 25.05, 25.00, 24.9, 24.3, 24.25, 24.21, 24.0, 23.9, 23.3, 23.1,
23.0, 22.2; HRMS (EI, m/z) calcd for C23H32O2 [M]+ 340.2397, found 340.2398; IR (film): 2934, 1712,
1624, 1469, 1433, 1245, 1195 cm-1.
Methyl 5-hexyl-2-(4-methoxyphenyl)undeca-2,4-dienoate (3g). A yellow oil; Yield: 58.8 mg,
(76%); E:Z = 5:1; Rf = 0.45 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 7.74 (d, J = 11.9 Hz, 2.5H),
7.26-7.28 (m, 2H), 7.14-7.16 (m, 5.0H), 6.86-6.92 (m, 8.0H), 6.58 (d, J = 11.8 Hz, 1H), 5.89 (d, J = 11.9
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Hz, 2.5H), 3.83 (s, 7.5H), 3.82 (s, 3H), 3.81 (s, 3H), 3.75 (s, 7.5H), 2.31 (t, J = 7.7 Hz, 5.0H), 2.25 (t, J
= 7.7 Hz, 2H), 2.16 (t, J = 7.6 Hz, 2H), 2.04 (t, J = 7.5 Hz, 5.0H), 1.21-1.46 (m, 70H), 0.84-0.92 (m,
21H); 13C NMR (100 MHz, CDCl3) δ 168.9, 168.8, 159.1, 158.8, 154,8, 152.5, 136.4, 132.6, 131.6,
131.3, 129.6, 129.2, 128.8, 127.8, 121.6, 113.7, 113.3, 55.3, 55.2, 52.0, 51.7, 38.2, 38.0, 31.8, 31.7, 31.6,
31.3, 30.9, 29.3, 29.3, 29.2, 29.0, 28.2, 28.0, 22.6, 14.1; HRMS (EI, m/z) calcd for C25H38O3 [M]+
386.2816, found 386.2812; IR (film): 2955, 1712, 1644, 1512, 1464, 1427, 1246 cm-1.
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Methyl 2-([1,1'-biphenyl]-4-yl)-5-hexylundeca-2,4-dienoate (3h). A colorless oil; yield: 73.5 mg
(85%); E:Z = 4:1; Rf = 0.46 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 12.0 Hz, 3.6H),
7.56-7.65 (m, 23.5H), 7.41-7.46 (m, 9.2H), 7.29-7.37 (m, 9.2H), 7.02 (d, J = 11.8 Hz, 1H), 6.64 (d, J =
11.8 Hz, 1H), 5.94 (d, J = 12.0 Hz, 3.6H), 3.85 (s, 3H), 3.78 (s, 10.8H), 2.34 (t, J = 7.7 Hz, 7.2H), 2.28
(t, J = 7.7 Hz, 2H), 2.18 (t, J = 7.5 Hz, 2H), 2.06 (t, J = 7.5 Hz, 7.2H), 1.22-1.48 (m, 92H), 0.83-0.93 (m,
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27.6H); C NMR (100 MHz, CDCl3) δ 168.6, 168.5, 155.6, 153.7, 140.9, 140.7, 140.2, 140.1, 137.8,
136.9, 134.6, 134.0, 130.8, 129.6, 129.2, 128.8, 128.0, 127.4, 127.3, 127.1, 127.0, 126.6, 121.6, 121.4,
52.1, 51.8, 38.3, 38.0, 31.8, 31.70, 31.66, 31.3, 31.0, 29.5, 29.4, 29.2, 29.1, 29.0, 28.2, 28.0, 22.6, 14.12,
14.08; HRMS (EI, m/z) calcd for C30H40O2 [M]+ 432.3023, found 432.3022; IR (film): 2958, 1712, 1623,
1487, 1466, 1434, 1242 cm-1.
Methyl 2-(4-chlorophenyl)-5-hexylundeca-2,4-dienoate (3i). A colorless oil; yield: 67.3 mg, 86%;
E:Z = 5:1; Rf = 0.51 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 12.0 Hz, 4.8H), 7.25-
7.35 (m, 11.6H), 7.14-7.16 (m, 11.6H), 6.93 (d, J = 11.8 Hz, 1H), 6.66 (d, J = 11.9 Hz, 1H), 5.81 (d, J =
12.0 Hz, 4.8H), 3.82 (s, 3H), 3.75 (s, 14.2H), 2.32 (t, J = 7.7 Hz, 9.6H), 2.25 (t, J = 7.7 Hz, 2H), 2.17 (t,
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J = 7.6 Hz, 2H), 2.05 (t, J = 7.4 Hz, 9.6H), 1.21-1.46 (m, 116H), 0.84-0.90 (m, 34.8H); C NMR (100
MHz, CDCl3) δ 168.1, 158.3, 154.5, 137.5, 137.2, 135.0, 134.0, 133.3,131.8, 129.1, 128.6, 128.4, 128.3,
128.1, 121.0, 52.1, 51.8, 38.3, 38.0, 31.8, 31.7, 31.6, 31.3, 30.9, 29.41, 29.36, 29.2, 29.1, 29.0, 28.2,
28.0, 22.6, 14.11, 14.07; HRMS (EI, m/z) calcd for C24H35ClO2 [M]+ 390.2320, found 390.2320; IR
(film): 2954, 1713, 1623, 1462, 1434, 1242, 1201 cm-1.
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Methyl 2-(4-bromophenyl)-5-hexylundeca-2,4-dienoate (3j). A colorless oil; yield: 84.5 mg
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(97%); E:Z = 7:1; Rf = 0.51 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 12.0 Hz, 6.8H),
7.48-7.51 (m, 13.6H), 7.45-7.47 (m, 2H), 7.19-7.22 (m, 2H), 7.08-7.10 (m, 13.6H), 6.94 (d, J = 11.8 Hz,
1H), 6.68 (d, J = 11.8 Hz, 1H), 5.81 (d, J = 12.0 Hz, 6.8H), 3.81 (s, 3H), 3.76 (s, 20.4H), 2.32 (t, J = 7.7
Hz, 13.6H), 2.25 (t, J = 7.7 Hz, 2H), 2.17 ((t, J = 7.6 Hz, 2H), 2.05 (t, J = 7.5 Hz, 13.6H), 1.21-1.46 (m,
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156H), 0.85-0.92 (m, 46.8H); C NMR (100 MHz, CDCl3) δ 168.0, 156.4, 154.6, 138.0, 137.2, 135.1,
134.5, 132.1, 131.4, 130.1, 129.3, 128.6, 128.3, 121.5, 121.4, 121.0, 52.1, 51.8, 38.3, 38.0, 31.8, 31.7,
31.6, 31.3, 31.0, 29.7, 29.4, 29.3, 29.2, 29.1, 29.0, 28.2, 28.0, 22.6, 14.1; HRMS (EI, m/z) calcd for
C24H35BrO2 [M]+ 434.1815, found 434.1816; IR (film): 2954, 1713, 1612, 1487, 1434, 1242 cm-1.
Ethyl 2-(2-fluorophenyl)-5-hexylundeca-2,4-dienoate (3k). A colorless oil; yield: 43.4 mg (58%);
E:Z > 20:1; Rf = 0.53 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 12.0 Hz, 1H), 7.28-
7.36 (m, 1H), 7.06-7.09 (m, 3H), 5.78 (d, J = 12.0 Hz, 1H), 4.22 (q, J = 7.10 Hz, 2H), 2.33 (t, J = 7.7 Hz,
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2H), 2.05 (t, J = 7.5 Hz, 2H), 1.20-1.47 (m, 20H), 0.84-0.92 (m, 6H); C NMR (100 MHz, CDCl3) δ
167.2, 161.5, 159.0, 156.1, 137.9, 132.4 (d, J = 3.5 Hz), 129.4 (d, J = 8.1 Hz), 124.1, 123.5 (dd, J = 6.4
Hz, J = 10.0 Hz), 121.1, 115.4 (d, J = 22 Hz), 60.8, 38.0, 31.6, 31.3, 29.3, 29.0, 28.9, 27.9, 22.6, 14.3,
14.1; HRMS (EI, m/z) calcd for C25H37FO2 [M]+ 388.2773, found 388.2771; IR (film): 2959, 1712, 1625,
1491, 1453, 1244, 1221, 1178, 1139 cm-1.
Ethyl 4-(5-hexyl-1-methoxy-1-oxoundeca-2,4-dien-2-yl)benzoate (3l). A colorless oil; yield: 55.6
mg (67%); E:Z = 6:1; Rf = 0.50 (PE:EA = 5:1); 1H NMR (400 MHz, CDCl3) δ 7.91-8.04 (m, 13.6H),
7.81 (d, J = 12 Hz, 5.8H), 7.39-7.55 (m, 13.6H), 7.00 (d, J = 11.8 Hz, 1H), 6.69 (d, J = 11.8 Hz, 1H),
5.77 (d, J = 12 Hz, 5.8H), 4.32 (q, J = 7.1 Hz, 2H), 4.23 (q, J = 7.1 Hz, 11.6H), 3.92 (s, 3H), 3.91 (s,
17.4H), 2.32 (t, J = 7.7 Hz, 11.6H), 2.27 (t, J = 7.8 Hz, 2H), 2.18 (t, J = 7.5 Hz, 2H), 2.03 (t, J = 7.4 Hz,
11.6H), 1.19-1.47 (m, 134H), 0.83-0.93 (m, 41.6H); 13C NMR (100 MHz, CDCl3) δ 167.7, 167.6, 167.0,
166.9, 156.0, 154.2, 139.3, 136.9, 136.0, 134.9, 134.6, 132.1, 131.6, 130.2, 129.8, 129.2, 128.8, 128.4,
128.3, 128.2, 127.9, 121.4, 120.9, 60.8, 52.1, 52.0, 38.2, 38.0, 31.8, 31.7, 31.6, 31.3, 30.9, 29.7, 29.4,
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29.3, 29.1, 29.0, 28.9, 28.1, 27.9, 22.6, 22.5, 14.2, 14.09, 14.05; HRMS (EI, m/z) calcd for C27H40O4
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[M]+ 428.2921, found 428.2923; IR (film): 2953, 1726, 1709, 1622, 1464, 1440, 1269, 1240 cm-1.
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Ethyl 5-hexyl-2-(4-nitrophenyl)undeca-2,4-dienoate (3m). A yellow oil; yield: 39.0 mg (47%);
E:Z = 10:1; Rf = 0.40 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 8.23 (d, J = 8.6 Hz, 22H), 8.19 (d,
J = 8.8 Hz, 2H), 7.85 (d, J = 12.1 Hz, 11H), 7.50 (d, J = 8.7 Hz, 2H), 7.40 (d, J = 8.6 Hz, 22H), 7.05 (d,
J = 12.0 Hz, 1H), 6.72 (d, J = 11.7 Hz), 5.78 (d, J = 12.1 Hz, 11H), 4.34 (q, J = 7.1 Hz, 2H), 4.24 (q, J =
7.1 Hz, 22H), 2.34 (t, J = 7.7 Hz, 22H), 2.29 (t, J = 8.0 Hz, 2H), 2.20 (t, J = 7.8 Hz, 2H), 2.06 (t, J = 7.5
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Hz, 22H), 1.21-1.52 (m, 246.6H), 0.84-0.92 (m, 66.3H); C NMR (100 MHz, CDCl3) δ 166.9, 158.0,
147.0, 142.8, 137.9,136.5,131.5, 128.3, 128.1, 127.6, 123,5, 123.1, 121.4, 120.5, 61.0, 38.2, 31.6, 31.4,
29.3, 29.1, 29.0, 28.0, 22.6, 14.3, 14.1, 14.0; HRMS (EI, m/z) calcd for C25H37NO4 [M]+ 415.2717,
found 415.2716; IR (film): 2957, 1709, 1621, 1601, 1346, 1241, 1187 cm-1.
o
Methyl (E)-5,5-diphenyl-2-(p-tolyl)penta-2,4-dienoate (3n). A white solid (m.p. = 148-152 C);
yield: 61.6 mg (87%); E:Z > 20:1; Rf = 0.20 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J =
11.8 Hz, 1H), 7.39-7.46 (m 3H), 7.16-7.28 (m, 12H), 6.71 (d, J = 11.8 Hz, 1H), 3.70 (s, 3H), 2.39(s, 3H);
13C NMR (100 MHz, CDCl3) δ 168.3, 150.6, 141.8, 139.0, 137.9, 137.6, 133.2, 132.3, 130.6, 130.3,
128.8, 128.4, 128.3, 128.3, 128.3, 128.3, 124.0, 52.1, 21.4; HRMS (ESI, m/z) calcd for C25H23O2
[M+H]+ 355.1693, found 355.1689; IR (film): 2951.6, 1708.6, 1261.0, 1234.1 cm-1.
Methyl (E)-5,5-diphenyl-2-(4-(trifluoromethyl)phenyl)penta-2,4-dienoate (3o). A white solid
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(m.p. = 108-110 oC); yield: 58.1 mg, 71%; E:Z > 20:1; Rf = 0.23 (PE:EA = 30:1); H NMR (400 MHz,
CDCl3) δ 7.67 (d, J = 8.1 Hz, 2H), 7.61 (d, J = 11.9 Hz, 1H), 7.44-7.46 (m, 5H), 7.25-7.28 (m, 5H),
7.15-7.18 (m, 2H), 6.60 (d, J = 11.9 Hz, 1H), 3.71 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 167.5, 152.4,
141.4, 139.2, 138.7, 131.6, 130.8, 130.6, 129.80 (q, J = 32.2 Hz), 128.9, 128.6, 128.4, 128.4, 28.3, 128.1
(q, J = 3.7 Hz), 124.2 (q, J = 272.1 Hz), 122.9, 52.2; HRMS (ESI, m/z) calcd for C25H20F3O2 [M+H]+
409.1410, found 409.1400; IR (film): 2918, 1709, 1433, 1324, 1264, 1236, 1165 cm-1.
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2-Methoxy-2-oxoethyl 5-hexyl-2-phenylundeca-2,4-dienoate (3p). A colorless oil; yield: 66.3 mg
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(80%); E:Z >20:1; Rf = 0.40 (PE:EA = 5:1); 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 12.0 Hz, 3.4H),
7.27-7.46 (m, 22.0H), 7.04 (d, J = 11.9 Hz, 1.0H), 6.78 (d, J = 11.9 Hz, 1.0H), 5.91 (d, J = 12.0 Hz,
3.4H), 4.75 (s, 2H), 4.69 (s, 6.8 H), 3.80 (s, 3H), 3.77 (s, 10.2H), 2.33 (t, J = 7.7 Hz, 6.8H), 2.27 (t, J =
7.7 Hz, 2H), 2.18 (t, J = 7.5 Hz, 2H), 2.05 (t, J = 7.4 Hz, 6.9H), 1.20-1.45 (m, 80H), 0.84-0.92 (m, 17H);
13C NMR (100 MHz, CDCl3) δ 168.6, 168.3, 167.4, 167.2, 156.4, 154.6, 138.7, 138.0, 136.0, 135.1,
130.5, 128.7, 128.6, 128.1, 128.0, 127.9, 127.5, 121.7, 121.4, 61.0, 60.8, 52.4, 51.2, 38.3, 38.0, 31.8,
31.7, 31.6, 31.4, 31.0, 29.7, 29.44, 29.40, 29.2, 29.1, 29.0, 28.2, 28.0, 22.6, 14.1; HRMS (EI, m/z) calcd
for C26H38O4 [M]+ 414.2765, found 414.2765; IR (film): 2953, 1767, 1717, 1621, 1462, 1378, 1203,
1116 cm-1.
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Ethyl (E)-2-((E)-3-((3r,5r,7r)-adamantan-1-yl)but-2-en-1-ylidene)decanoate (3q). A colorless
oil; yield: 41.7 mg (54%); Rf = 0.47 (PE:EA = 20:1); 1H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 11.7 Hz,
1H), 6.16 (d, J = 11.8 Hz, 1H), 4.21 (q, J = 7.1 Hz, 2H), 2.39-2.43 (m, 2H), 2.04 (s, 3H), 1.86 (s, 3H),
1.66-1.76 (m, 12H), 1.27-1.32 (m, 15H), 0.88 (t, J = 6.7 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 168.8,
155.8, 135.0, 117.1, 60.2, 40.6, 39.1, 36.9, 31.9, 29.5, 29.4, 29.4, 29.3, 28.6, 26.6, 22.7, 14.4, 14.2, 13.0;
HRMS (ESI, m/z) calcd for C26H43O2 [M+H]+ 387.3258, found 387.3249; IR (film): 2916, 1703, 1624,
1452, 1255, 1123, cm-1.
Dimethyl 2-((E)-3-((3r,5r,7r)-adamantan-1-yl)but-2-en-1-ylidene)malonate (3r). A white solid
(m.p. = 71-74 oC); yield: 52.2 mg (82%); Rf = 0.42 (PE:EA = 10:1); 1H NMR (400 MHz, CDCl3) δ 7.80
(d, J = 12.1 Hz, 1H), 6.36 (d, J = 12.1 Hz, 1H), 3.86 (s, 3H), 3.80 (s, 3H), 2.04 (s, 3H), 1.93 (s, 3H),
1.65-1.76 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 166.4, 165.6, 163.7, 142.3, 122.7, 117.3, 52.3, 52.2,
40.3, 39.7, 36.7, 28.4, 13.3; HRMS (ESI, m/z) calcd for C19H27O4 [M+H]+ 319.1904, found 319.1898;
IR (film): 2905, 1719, 1616, 1435, 1384, 1255, 1213, 1151 cm-1.
Ethyl (2E,4E)-5-((3r,5r,7r)-adamantan-1-yl)-2-benzylhexa-2,4-dienoate (3s). A colorless oil;
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yield: 36.4 mg (50%); Rf = 0.39 (PE:EA = 20:1); H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 11.7 Hz,
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1H), 7.14-7.24 (m, 5H), 6.32 (dd, J = 0.8Hz, J = 11.7 Hz, 1H), 4.16 (q, J = 7.1Hz, 2H), 3.79 (s, 2H),
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2.03 (s, 3H), 1.90 (s, 3H), 1.64-1.75 (m, 12H), 1.24 (t, J = 7.1Hz, 3H); C NMR (100 MHz, CDCl3) δ
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168.5, 157.5, 140.4, 136.3, 129.1, 128.4, 128.3, 125.9, 117.2, 60.5, 40.6, 39.3, 36.9, 32.5, 25.5, 14.3,
13.2; HRMS (ESI, m/z) calcd for C25H33O2 [M+H]+ 365.2475, found 365.2469; IR (film): 2905, 1703,
1623, 1452, 1257, 1190, 1082 cm-1.
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Competition Experiments of the Diazo Compounds. A 10 mL oven-dried Schlenk flask was
charge with [Cp*Ru(cod)Cl] (1.0 mg, 0.0025 mmol, 2.5 mol %) under nitrogen. Then dry THF (0.3 mL)
was added using a syringe. Cyclopropene (1a, 0.13 mmol, 1.3 equiv) and diazo compounds (2a 0.05
mmol and 2g 0.05 mmol solved in 0.2 mL THF) were successively added by syringe. The reaction was
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heated at 60 C with stirring for 0.5 min, then, cooled to 0 C immediately. The reaction mixture was
filtered through a short column of silica gel eluted with chloroform. Solvent was then removed in vacuo
to leave a crude mixture. The ratio of the products was determined by 1H NMR (400 MHz).
Control Experiments. A 10 mL oven-dried Schlenk flask was charge with [Cp*Ru(cod)Cl] (1.0
mg, 0.0025 mmol, 2.5 mol %) under nitrogen. Then dry THF (0.5 mL) was added using a syringe.
Substrate (1d, 2a or 2m, 0.1 mmol) was successively added by syringe. The reaction was heated at 60 oC
with stirring for 4 h, then, cooled to room temperature. The reaction mixture was filtered through a short
column of silica gel, eluted with chloroform. Solvent was then removed in vacuo to leave a crude
mixture. The ratio of the products was determined by 1H NMR (400 MHz).
The Effect of Alkenyl Groups on the Reaction. A 10 mL oven-dried Schlenk flask was charge
with [Cp*Ru(cod)Cl] (1.0 mg, 0.005 mmol, 2.5 mol %) under nitrogen. Then dry THF (0.3 mL) was
added using a syringe. Cyclopropene 1a (0.13 mmol, 1.3 equiv) and the olefin additive (0.13 mmol)
were solved in THF (0.2 mL) and the solution and diazo compound (0.20 mmol, 1.0 equiv) were
o
successively added by syringe. The reaction was heated at 60 C with stirring for 2 min or 4 h, then
cooled to room temperature immediately. The reaction mixture was filtered through a short column of
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silica gel, eluted with chloroform. Solvent was then removed in vacuo to leave a crude mixture. The
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ASSOCIATED CONTENT
Supporting Information
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Copies of 1H and 13C spectra for all products. This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Email: wangjb@pku.edu.cn.
ORCID
Jianbo Wang: 0000-0002-0092-0937
Author Contributions
§BW and HY contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The project is supported by National Basic Research Program of China (973 Program, No.
2015CB856600) and NSFC (Grant 21472004 and 21332002). We thank Prof. Zhenhua Zhang (China
Agricultural University) for providing azide reagents (supported by the National Key Technologies
R&D Program of China, 2015BAK45B01, CAU).
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