Ru(II)-Catalyzed Cross-Coupling of Cyclopropenes with Diazo

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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

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*,†,‡ †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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The Journal of Organic Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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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 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 1,1difluoroolefins 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

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-2phenylacetate 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(pcymene)]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). 3 Environment ACS Paragon Plus


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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). Table 1. Optimization of the Reaction Conditions

entry

solvent

1a:2a

cat.

yield (%)a

E/Zb

1

MeCN

1:1

CuI

10

ndc

2

MeCN

1:1

AuCl

19

nd

3d

MeCN

1:1

AuPPh3Cl

21

nd

4

PhMe

1:1

[Rh(cod)Cl]2

12

nd

5

PhMe

1:1

[RuCl2(p-cymene)]2

43

3:1

6

PhMe

1:1

Ru(PPh3)3Cl2

19

4:1

7

PhMe

1:1

CpRu(PPh3)2Cl

21

10:1

8

PhMe

1:1

[RuCl2(benzene)]2

37

2.5:1

9

PhMe

1:1

[Cp*Ru(cod)Cl]

72

3:1

10e

THF

1.3:1

[Cp*Ru(cod)Cl]

98(88f)

5:1

11g

THF

1.3:1

none

0

--

aNMR d5

yield. bDetermined by 1H NMR (400 MHz). cnd: not determined.

mol% AgOTf was used. e2.5 mol% catalyst was used. fIsolated yield.

gThe

substrates remained unchanged.


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With the optimized reaction conditions, the scope of cyclopropenes was then examined. As illustrated in Scheme 2, various 3,3-disubstituted cyclopropenes reacted smoothly with methyl 2-diazo2-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. 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

mL) at 60 oC. 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. 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

(1.0 mL) at 60 oC. All of the yields refer to the isolated products by column chromatography. The ratio of E:Z was determined by 1H NMR. bThe reaction temperature was 70 oC. c2.0 equiv of cyclopropene was used. dThe reaction was carried in PhMe (1.0 mL) at 50 oC. eThe yield was estimated by 1H NMR (400 MHz). f 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. 7 Environment ACS Paragon Plus


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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. 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

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 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. 12 Environment ACS Paragon Plus

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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. 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, 10.6H), 1.20-1.46 (m, 118H), 0.84-0.92 (m, 42H); 13C 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, 13 Environment ACS Paragon Plus


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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. Methyl 5,5-dicyclohexyl-2-phenylpenta-2,4-dienoate (3b). A colorless oil; yield: 47.2 mg, (67%); E:Z = 8:1; Rf = 0.52 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 7.93 (d, J = 12.0 Hz, 7.6H), 7.307.40 (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, 172H);

13C

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 oC); yield: 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 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); 13C 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 (m.p. = 118-121 oC); yield: 28.8 mg (43%); Rf = 0.46 (PE:EA = 20:1); 1H 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 (m.p. = 119-122 oC); yield: 12.6 mg (19%); Rf = 0.49 (PE:EA = 20:1); 1H NMR (400 MHz, CDCl3) δ 14 Environment ACS Paragon Plus

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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 (s, 3H), 1.66-1.74 (m, 12H);

13C

NMR (100 MHz, CDCl3) δ 168.6, 156.3, 139.1, 135.5, 130.7, 128.2,

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]+ 337.2162, found 337.2156; IR (film): 2905, 1712, 1617, 1449, 1433, 1202 cm-1. 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), 7.287.40 (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%); E:Z = 5:1; Rf = 0.50 (PE:EA = 30:1); 1H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 11.9 Hz, 5.0H), 7.287.39 (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 15 Environment ACS Paragon Plus


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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. 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, 27.6H);

13C

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), 7.257.35 (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, 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); 13C 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. 16 Environment ACS Paragon Plus

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Methyl 2-(4-bromophenyl)-5-hexylundeca-2,4-dienoate (3j). A colorless oil; yield: 84.5 mg (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, 156H), 0.85-0.92 (m, 46.8H); 13C 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), 7.287.36 (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, 2H), 2.05 (t, J = 7.5 Hz, 2H), 1.20-1.47 (m, 20H), 0.84-0.92 (m, 6H);

13C

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, 17 Environment ACS Paragon Plus


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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 [M]+ 428.2921, found 428.2923; IR (film): 2953, 1726, 1709, 1622, 1464, 1440, 1269, 1240 cm-1. 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 Hz, 22H), 1.21-1.52 (m, 246.6H), 0.84-0.92 (m, 66.3H);

13C

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. Methyl (E)-5,5-diphenyl-2-(p-tolyl)penta-2,4-dienoate (3n). A white solid (m.p. = 148-152 oC); 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 (m.p. = 108-110 oC); yield: 58.1 mg, 71%; E:Z > 20:1; Rf = 0.23 (PE:EA = 30:1); 1H 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 (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. 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; yield: 36.4 mg (50%); Rf = 0.39 (PE:EA = 20:1); 1H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 11.7 Hz, 19 Environment ACS Paragon Plus


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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), 2.03 (s, 3H), 1.90 (s, 3H), 1.64-1.75 (m, 12H), 1.24 (t, J = 7.1Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 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. 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 heated at 60 oC with stirring for 0.5 min, then, cooled to 0 oC 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 successively added by syringe. The reaction was heated at 60 oC 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 yield was determined by 1H NMR (400 MHz). ASSOCIATED CONTENT Supporting Information 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: [email protected]. 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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REFERENCES (1) (a) Serratosa, J. F. F.; Valls, J. Chem. Commun. 1970, 721-722. (b) Kulkowit, S.; McKervey, M. A. J. C. S. Chem. Comm. 1978, 1069-1070. (c) Doyle, M. P.; Hu, W.; Philips, I. M. Org. Lett. 2000, 2, 1777-1779. (d) Li, G.-Y.; Che, C.-M. Org. Lett. 2004, 6, 1621-1623. (e) Xia, Y.; Liu, Z.; Xiao, Q.; Qu, P.; Ge, R.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 2012, 51, 5714-5717. (f) Zhu, C.; Xu, G.; Liu, K.; Qiu, L.; Peng, S.; Sun, J. Chem. Commun. 2015, 51, 12768-12770. (g) Zhu, C.; Qiu, L.; Xu, G.; Li, J.; Sun, J. Chem. Eur. J. 2015, 21, 12871-12875. (2) (a) Hodgson, D. M.; Angrish, D. Chem. Eur. J. 2007, 13, 3470-3479. (b) Hansen, J. H.; Parr, B. T.; Pelphrey, P.; Jin, Q.; Autschbach, J.; Davies, H. M. L. Angew. Chem. Int. Ed. 2011, 50, 2544-2548. (c) Zhang, D.; Xu, G.; Ding, D.; Zhu, C.; Li, J.; Sun, J. Angew. Chem. Int. Ed. 2014, 53, 1107011074. (d) Zhu, C.; Xu, G.; Ding, D.; Lin, Q.; Sun, J. Org. Lett. 2015, 17, 4244-4247. (3) (a) Herndon, J. W., Wang, H. J. Org. Chem. 1998, 63, 4564. (b) Barluenga, J.; López, L. A.; Löber, O.; Tomás, M.; García-Granda, S.; Alvarez-Rúa, C.; Borge, J. Angew. Chem. Int. Ed. 2001, 40, 3392-3394. (c) Hu, F.; Yang, J.; Xia, Y.; Ma, C.; Xia, Y.; Zhang, Y.; Wang, J. Org. Chem. Front. 2015, 2, 1450-1456. (d) Zhang, Z.; Yu, W.; Wu, C.; Wang, C.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 2016, 55, 273-277. (4) (a) Barluenga, J.; Riesgo, L.; Vicente, R.; López, L. A.; Tomás, M. J. Am. Chem. Soc. 2008, 130, 13528-13529. (b) Bray, C. V.-L.; Dérien,, S.; Dixneuf, P. H. Angew. Chem. Int. Ed. 2009, 48, 14391442. (c) Moulin, S.; Zhang, H.; Raju, S.; Bruneau, C.; Dérien, S. Chem. Eur. J. 2013, 19, 32923296. (5) For recent reviews on cyclopropenes, see: (a) Rubin, M.; Rubina, M.; Gevorgyan, V. Synthesis 2006, 1221-1245. (b) Rubin, M.; Rubina, M.; Gevorgyan, V. Chem. Rev. 2007, 107, 3117-3179. (c) Zhu, Z.-B.; Wei, Y.; Shi, M. Chem. Soc. Rev. 2011, 40, 5534-5563. (d) Miege, F.; Meyer, C.; Cossy, J.


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Beilstein J. Org. Chem. 2011, 7, 717-734. (e) Jia, M.; Ma, S. Angew. Chem. Int. Ed. 2016, 55, 91349166. (6) For examples of C−H insertions, see: (a) Müller, P.; Gränicher, C. Helv. Chim. Acta 1993, 76, 521534. (b) Zhu, Z.-B.; Shi, M. Org. Lett. 2009, 11, 5278-5281. (c) Archambeau, A.; Miege, F.; Meyer, C.; Cossy, J. Angew. Chem., Int. Ed. 2012, 51, 11540-11544. (d) Li, C.; Zeng, Y.; Wang, J. Tetrahedron Lett. 2009, 50, 2956-2959. (7) For the examples of O−H insertions, see: (a) Bauer, J. T.; Hadfield, M. S.; Lee, A.-L. Chem. Commun. 2008, 6405-6407. (b) Hadfield, M. S.; Bauer, J. T.; Glen, P. E.; Lee, A.-L. Org. Biomol. Chem. 2010, 8, 4090-4095. (8) For the examples of cyclopropanations, see: (a) Zhou, Y.; Trewyn, B. G.; Angelici, R. J.; Woo, L. K. J. Am. Chem. Soc. 2009, 131, 11734-11743. (b) Miege, F.; Meyer, C.; Cossy, J. Angew. Chem., Int. Ed. 2011, 50, 5932-5937. (9) (a) Zhang, H.; Li, C.; Xie, G.; Wang, B.; Zhang, Y.; Wang, J. J. Org. Chem. 2014, 79, 6286-6293. (b) Zhang, H.; Wang, B.; Wang, K.; Xie, G.; Li, C.; Zhang, Y.; Wang, J. Chem. Commun. 2014, 50, 8050-8052. (c) Zhang, H.; Wang, K.; Wang, B.; Yi, H.; Hu, F.; Li, C.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 2014, 53, 13234-13238. (d) Zhang, H.; Wang, B.; Yi, H.; Zhang, Y.; Wang, J. Org. Lett. 2015, 17, 3322-3325. (e) Zhang, H.; Wang, B.; Yi, H.; Sun, T.; Zhang, Y.; Wang, J. Chem. Commun. 2016, 52, 13285-13287 (10) While our work was undergoing, López, Vicente and coworkers reported Zinc-catalyzed crosscoupling of cyclopropenes and diazo compounds, see: Mata, S.; González, M. J.; González, J.; López, L. A.; Vicente, R. Chem. Eur. J. 2017, 23, 1013-1017. (11) Wang, K.; Chen, S.; Zhang, H.; Xu, S.; Ye, F.; Zhang, Y.; Wang, J. Org. Biomol. Chem. 2016, 14, 3809-3820.


Ru(II)-Catalyzed Cross-Coupling of Cyclopropenes with Diazo

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