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A 1,2-Dicarbadodecaborane(12)-1,2-Dithiolate Chelating Ruthenium

Oct 4, 2017 - Department of Chemistry, College of Science, Tianjin University, Tianjin 300350, People's Republic of China. ‡ Collaborative Innovatio...
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A 1,2-Dicarbadodecaborane(12)-1,2-Dithiolate Chelating Ruthenium Carbene Catalyst for Highly Z Selective Olefin Metathesis Tao Wang,†,‡ Yulian Duan,†,‡ Xinying Liu,†,‡ Qingxiao Xie,†,‡ Weijie Guo,†,‡ Xiaobo Yu,†,‡ Shutao Wu,†,‡ Jianhui Wang,*,†,‡ and Guiyan Liu*,§ †

Department of Chemistry, College of Science, Tianjin University, Tianjin 300350, People’s Republic of China Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 30072, People’s Republic of China § Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic−Organic hybrid Functional Material Chemistry, College of Chemistry, Tianjin Normal University, Tianjin, 300387, People’s Republic of China ‡

S Supporting Information *

ABSTRACT: A highly Z selective olefin metathesis ruthenium carbene catalyst containing a 1,2-dicarbadodecaborane(12)-1,2-dithiolate ligand was synthesized, and the structure was determined by single-crystal X-ray diffraction. Due to the large steric hindrance and strong electronwithdrawing effects of the carborane ligand, the new ruthenium complex is more stable than previously reported Ru catalysts which contain benzene-1,2-dithiolate ligands. The new ruthenium carbene catalyst can catalyze cross-metathesis (CM) reactions of terminal alkenes with (Z)-but-2-ene-1,4diol and CM reactions of other terminal alkenes to give highly Z selective products in moderate to good yields. In addition, the catalyst was also able to catalyst a ring-closing metathesis (RCM) reaction to give a macrocyclic ring compound with a (Z)olefin structure as the major product. Like other ruthenium carbene catalysts, the new complex tolerates many different functional groups.

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Chart 1. Z-Selective Catalysts for Olefin Metathesis

INTRODUCTION The olefin metathesis reaction is a simple, fast, and efficient tool for constructing complex molecules. These reactions usually produce few byproducts, which is important from a green chemistry standpoint. Olefin metathesis has been widely applied to many synthetic fields, including synthetic chemicals,1 pharmaceuticals and biotechnology,2 and functional polymer materials.3 The success of olefin metathesis has stemmed from the discovery of air- and moisture-stable ruthenium carbene catalysts which are tolerant to many different functional groups.4 These catalysts are highly selective for (E)-olefin products in cross-metathesis (CM) reactions and in the construction of macrocyclic compounds via ring-closing metathesis (RCM) reactions. However, since many natural products and pharmaceutical molecules5 contain (Z)-olefin structures, a critical challenge for olefin metathesis reactions is the production of (Z)-olefin products. In this context, some new metathesis catalysts with Z selectivity have been developed. For example, the molybdenum aryloxy complex 1 (Chart 1) with a pyrryl ligand has been found to give some (Z)-olefin products in ring-opening crossmetathesis (ROCM) reactions.6 Subsequently, a series of Zselective complexes containing molybdenum or tungsten were developed using a similar structure,7 and these complexes were successfully applied to the synthesis of macrocyclic molecules © XXXX American Chemical Society

Received: July 23, 2017

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DOI: 10.1021/acs.organomet.7b00556 Organometallics XXXX, XXX, XXX−XXX

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through CM and RCM reactions.8a,b Some molybdenum- and tungsten-based catalysts have been shown excellent Z selectivity and high reactivity, especially in sterically hindered systems. In addition to biological products, a tungsten oxo alkylidene catalyst has been demonstrated to promote ring-closing metathesis reactions to form 45-membered macrocyclic compounds with Z selectivity. 8c However, like other molybdenum and tungsten complexes, the functional group compatibility of these newly developed catalysts is poor, and some common functional groups such as hydroxyl and carboxylic groups can deactivate the catalysts, which seriously restricts their applications to organic synthesis. However, this work on molybdenum and tungsten catalysts has enhanced the development of ruthenium carbene catalysts. In 2011, the ruthenium-based Z-selective olefin metathesis catalyst 2 (Chart 1) was developed.9 Complex 2 can catalyze CM reactions of terminal olefins to give (Z)-olefin dimer products with excellent selectivities. Further studies have shown that complex 3 (Chart 1),10 which is formed by replacing the carboxyl in 2 with a nitrate ligand, has better catalytic activity and selectivity than 2. Using a more hindered NHC ligand also increases the activity and Z selectivity of the catalyst.11 These Z-selective catalysts can be used in a wide variety of CM reactions, including the synthesis of industrial products.12 In addition, these rutheniumbased catalysts tolerate many functional groups and efficiently convert olefins in different solvents and at various temperatures while maintaining excellent Z selectivity.13 The development of these Z-selective ruthenium carbene catalysts has further expanded the range of olefin metathesis reactions. In the quest to further expand the scope of metathesis reactions, complex 4a (Chart 1), in which the two chlorides of the Hoveyda−Grubbs second-generation catalyst were substituted with a benzenedithiolate ligand, was developed in 2013.14 This catalyst was found to catalyze the ring-opening metathesis reaction of a substrate with a tension ring to give a Z-selective product. Later on, complexes 4b−e (Chart 1) with substituted benzenedithiolate ligands were found to have even better stabilities and catalytic activities.15 These complexes all have good functional group tolerance and give highly selective (Z)-olefin products in the CM reactions of (Z)-but-2-ene-1,4diol and terminal alkenes. These disulfide chelating ruthenium catalysts have simple structures which are easily constructed, and they have good functional group tolerance. Thus, they have good prospects for future applications.15,16 However, these complexes are prone to decomposition during the catalytic process. The sulfide at the position opposite the N-heterocyclic carbene ligands has a higher electron density than the other sulfide, and it can nucleophilically add to the carbene carbon linked to ruthenium center to form a deactivated complex.14−17 The energy barrier of this reaction is relatively low, and the reaction competes with the olefin metathesis reaction.15 Therefore, the catalyst can only be used at low temperatures, which is a problem for some sterically large, electron-deficient olefin substrates. Furthermore, the catalytic activity of these Ru carbene catalysts needs to be improved.18 Good conversions and selectivities have only been reported for catalyst loadings of 5 mol % and higher. Therefore, there is still a great need to develop Z-selective disulfide chelating ruthenium catalysts with good stabilities and high catalytic activities.

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RESULTS AND DISCUSSION Carborane is a polyhedron composed of carbon and boron atoms. Due to the special bonding characteristics of boron, the electrons are delocalized over the whole polyhedron and the compound is as stable as benzene. However, the electrondeficient property of borane gives carborane a stronger electron-withdrawing property than benzene when it is functionalized at its carbon atoms.19,20 For example, the acidity of 1-hydroxy-1,2-dicarbadodecaborane, in which the hydroxyl group is linked to a 1,2-dicarbadodecaborane, is between those of 4-nitrophenol and 2,4-dinitrophenol.21 Moreover, carborane processes a three-dimensional polyhedral structure which is more sterically hindered than the planar structure of a benzene ring,22 and carboranes have often been used in ligand design and catalysis.23 1,2-Dicarbadodecaborane has large space constraints and has an electron-withdrawing effect when contacting at carbon atoms. These two properties can increase the stability of the catalyst by weakening the nucleophilic properties of sulfur atoms and inhibiting the nucleophilic reaction of sulfur atoms to benzylidene carbon. A similar example for steric protection against nucleophilic attack at the benzylidene carbon has been reported by Fogg et al.24 In this context, a new ruthenium carbene catalyst bearing a 1,2dicarbadodecaborane(12)-1,2-dithiolate ligand was synthesized and the catalytic activity of this complex is reported herein. The new Ru complex containing a 1,2-dicarbadodecaborane(12)-1,2-dithiolate ligand could be synthesized via two different pathways, which are depicted in Scheme 1. In the first Scheme 1. Synthesis of 1,2-Dcarbadodecaborane(12)-1,2dithiolate Chelating Z-Selective Ruthenium Carbene Catalyst 9

pathway, 1,2-dicarbadodecaborane(12)-1,2-dithiol was first converted to the corresponding zinc salt (6) in high yield (87%). The zinc salt 6 was then treated with the Hoveyda− Grubbs second-generation catalyst (8) in THF at room temperature to give the desired product 9 in a 65% yield. In the second pathway, 1,2-dicarbadodecaborane(12)-1,2-dithiol was treated with sodium tert-butoxide (1:2 equiv) in CH3OH at room temperature to quantitatively give sodium 1,2-dicarbadodecaborane(12)-1,2-dithiolate (7) in a high yield (93%). The sodium dithiolate 7 and 8 were stirred in THF at 22 °C for 2 h to give the ruthenium-based complex 9 as an orange-brown solid in good yield (72%). The 1H NMR spectra of the complex contained singlet peaks at δ 1.43−2.60 and 15.55 ppm, which correspond to the carborane and benzylidene carbene protons, respectively. This indicates that the ligand exchange was successful. A single crystal of complex 9 was grown by slow evaporation from a CH2Cl2/n-hexane mixture solution at −5 °C under N2. The structure of 9 determined by single-crystal X-ray diffraction is shown in Figure 1. The arrangement of the ligand around the B

DOI: 10.1021/acs.organomet.7b00556 Organometallics XXXX, XXX, XXX−XXX

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Organometallics

of treatment, 39% of the compound remained intact. In contrast, 4c decomposed quickly during the first 2 h and after 9 h only 24% remained. These results show that complex 9 is more thermally stable than 4c. For both complexes, there were no further declines in concentrations between 10 and 12 h of treatment. This is probably due to the achievement of a chemical equilibrium between the degraded complex and the remaining catalyst. Next, the catalytic activity and Z selectivity of 9 for CM reactions of terminal olefins and (Z)-but-2-ene-1,4-diol were tested, and the results are shown in Table 1. The CM reactions in THF at 60 °C in the presence of 9 (5.0 mol %) under N2 proceeded smoothly to give an array of (Z)-alkenyl alcohols.

Figure 1. Perspective view of 9. Ellipsoids are drawn at the 50% probability level. For clarity, the solvents and all hydrogen atoms have been omitted. See the Supporting Information for detailed bond lengths and angles.

Table 1. Z-Selectivity Study of Ru-Based Catalyst 9 in CM Reactions of Different Terminal Alkenes and (Z)-But-2-ene1,4-diol

metal center is similar to that found in Hoveyda complexes.15,18 Compound 9 has a slightly deformed trigonal-bipyramidal structure with the NHC carbene, two sulfides, the phenyl oxide, and the benzylidene carbene ligand arranged around the Ru metal center. The bond distance between the oxygen and the Ru center Ru(1)−O (1) is 2.2949(19) Å which is longer than that in 4a (2.2769(17) Å) and 4c (2.273(5) Å). The Ru(1)− C(12) (2.065(3) Å), Ru(1)−C(22) (1.830(3) Å), and Ru(1)− S(1) (2.2813(7) Å) bond distances are very close to those in complexes 4a,c. However, the Ru(1)−S(2) (2.3215(7) Å) bond distance is slightly longer than those in 4a (2.2933(6) Å) and 4c 92.295(2) Å). The S(1)−Ru−S(2) (91.75(2)°), S(2)− Ru(1)−O(1) (172.02(5)°), C(22)−Ru(1)−S(1) (93.52(9)°), C(22)−Ru(1)−O(1) (78.89(10)°), and C(12)−Ru(1)−S(2) (150.21(8)°) bond angles are all larger than the corresponding angles in 4a,c, whereas the C(22)−Ru(1)−C(12) (99.56(11)°), O(1)−Ru(1)−S(1) (88.62(5)°), C(12)− Ru(1)−O(1) (98.08(9)°), C(22)−Ru(1)−S(1) (110.23(8)°), and C(12)−Ru(1)−S(1) (85.51(8)°) bond angles are smaller than those in 4a,c. These results show that the introduction of a 1,2-dicarbadodecaborane(12)-1,2-dithiol tag changed the structure of the catalytic center, which may result in better stability and catalytic activities for 9. To test this hypothesis, the thermal stability of 9 was tested and the results are shown in Figure 2. The study was performed at 70 °C under N2 using nonpretreated d6-DMSO (0.0131 mol/L, 1 mL) as the solvent. The degradation process was monitored by 1H NMR using benzophenone (7.5 μmol) as the internal standard. Complex 9 decomposed slowly, and after 9 h

a

Reaction conditions: reaction duration, 6 h; solvent, THF (0.5 mL); temperature, 60 °C; Ru complex, 5 mol %; terminal alkenes, 1.0 equiv; (Z)-but-2-ene-1,4-diol, 2.0 equiv; under N2. bConversions and Z:E ratios were determined by analysis of 1H NMR spectra of the mixtures. c Yields are based on isolated pure products.

The products all had high stereoselectivities (Z:E 96:4 to 99:1) and were obtained in medium to high yields (50−83%). These yields and selectivities are comparable to or better than those for 4a−e for similar reactions. Like other rutheniumbased olefin metathesis catalysts, 9 tolerates many different functional groups. For example, CM occurred between (Z)-but2- ene-1,4-diol and terminal alkenes with hydroxyl (11 and 13), ketone (13), aldehyde (12), and unprotected amino (18) groups. In addition, the CM reaction was successful for olefins with different chain lengths (15−17) and longer chains gave higher yield. Nonconjugated olefins with alkyl chains (10−18) were more active and had better Z-product selectivity than conjugated olefins with aryl groups (19 and 20). During the catalyst 9 mediated CM reactions between terminal olefins and (Z)-but-2-ene-1,4-diol, occasionally small amounts of terminal olefin homocoupled products were observed, indicating that the reactivity of 9 is different from those of 4a−e. Therefore, homometathesis reactions of terminal olefins were investigated using 9 as the catalyst (Table 2, 21−23). The dimeric (Z)-olefin products were

Figure 2. Stability test of complex 9 and 4c in d6-DMSO at 70 °C under N2, as monitored by 1H NMR using benzophenone as the internal standard. C

DOI: 10.1021/acs.organomet.7b00556 Organometallics XXXX, XXX, XXX−XXX

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Organometallics Table 2. Z-Selective Cross-Metathesis of Ru-Based Catalyst for Terminal Olefins

tolerate many different functional groups and is suitable for many substrates. The introduction of a 1,2-dicarbadodecaborane(12)-1,2-dithiolate ligand to the Ru center improved the stability and reactivity of the catalyst. In addition, this work provides a theoretical basis for the synthesis and design of other stable and efficient metal catalysts. Further studies on the application of this 1,2-dicarbadodecaborane(12)-1,2-dithiolate chelating Ru carbene catalyst to the synthesis of functional molecules and polymers are currently ongoing in our laboratories.

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EXPERIMENTAL SECTION

General Information. 1H NMR and 13C NMR spectra were acquired in CDCl3 on Bruker AVANCE III 600 MHz and Bruker AVANCE III 400 MHz spectrometers. If not otherwise noted, chemical shift values of are reported as values in ppm relative to residual CDCl3 (J = 7.26 Hz) for 1H NMR spectra, relative to CDCl3 (77.1 ppm) for 13C NMR spectra. Multiplicities are described using the following abbreviations: singlet (s), doublet (d), doublet of doublets (dd), triplet (t), quartet (q), and multiplet (m). Coupling constants (J) are quoted in Hz at 400 or 600 MHz for 1H. Gas chromatography−mass spectroscopy (GC-MS) analyses were performed on a Thermo Exactive Orbitrap apparatus. High-resolution mass spectra were provided using Bruker Daltonics matrix assisted laser desorption tandem time-of-flight mass spectrometry (Autoflex tof/tof III). GC-MS spectra were acquired in acetone on a Shimadzu GCMS-QP2010 SE instrument. High-resolution mass spectra (HRMS) were obtained on a JEOL JMS-DX303 instrument. Elemental analyses were performed by the Elemental Analysis Section of Tianjin University. Materials and Methods. Unless otherwise noted, all reactions were performed under an atmosphere of dry N2 with oven-dried glassware and anhydrous solvents with standard drybox or vacuum line techniques. Toluene, THF, hexane, and Et2O were distilled from sodium/benzophenone under a N2 atmosphere. Methanol was distilled over MgSO4. CH2Cl2 was dried over CaH2 and distilled prior to use. All other solvents were dried over 4−8 Å mesh molecular sieves (Aldrich) and were either saturated with dry argon or degassed before use. Reactions were monitored by analytical thin-layer chromatography on 0.20 mm Yantai Huagong silica gel plates. Silica gel (200− 300 mesh, from Yantai Huagong Co.) was used for flash chromatography. CDCl3 and DMSO-d6 were purchased from TCI and used as received. 1-But-3-enoxyl 4-nitrobenzoate,25 N-(5hexenyl)phthalimide, 26 1-[4-hydroxy-3-(2-propen-1-yl)phenyl]ethanone,27 2-propenyl benzoate,28 5-hexenyl benzoate,29 10-undecenyl benzoate,30 1,2-dicarbadodecaborane(12)-1,2-dithiol (5),31 Nallyl-4-nitroaniline,32 2-(allylthio)phenol,33 2-(but-3-en-1-yloxy)benzaldehyde34 were prepared by literature procedures. All other chemicals or reagents were obtained from commercial sources. Preparation of Zinc 1,2-Dicarbadodecaborane(12)-1,2-dithiolate (6). In an N2-filled glovebox, a solution of Zn(OAc)2· 2H2O (878 mg, 4.00 mmol, 2.0 equiv) and ethylenediamine (0.40 mL, 6.00 mmol, 3.0 equiv) in i-PrOH (8 mL) was transferred to a vial containing 5 (416.6 mg, 2.00 mmol, 1.0 equiv), and the resulting mixture was stirred for 1 h at 22 °C. The precipitated solid was filtered, washed with methanol (5.0 mL) and hot chloroform (5.0 mL), and dried under vacuum to afford zinc 1,2-dicarbadodecaborane(12)-1,2dithiolate (6; 472.7 mg, 1.74 mmol, 87% yield) as a white solid. Preparation of Sodium 1,2-Dicarbadodecaborane(12)-1,2dithiolate (7). In an N2-filled glovebox, a solution of sodium tertbutoxide (427.1 mg, 4.40 mmol, 2.2 equiv) in methanol (8.2 mL) was transferred to a vial containing 5 (416.6 mg, 2.00 mmol, 1.0 equiv), and the resulting mixture was stirred for 30 min at 50 °C. The mixture was cooled to room temperature followed by evaporation of solvent under vacuum. The residue was transferred to a fritted funnel and washed with tetrahydrofuran (10 mL). After removal of solvents in vacuo, sodium 1,2-dicarbadodecaborane(12)-1,2-dithiolate (7) was obtained as a white solid (469.1 mg, 1.86 mmol, 93% yield) and used directly without purification. 13C{1H} NMR (100 MHz, MeOD): δ

a

Except where noted, the catalytic reactions were performed in THF (0.5 mL) at 60 °C for 8 h under nitrogen in the presence of 9 (10 mol %). Yields correspond to isolated and purified products. bConversions and Z:E ratios were determined by analysis of 1H NMR spectra of the unpurified mixtures. cIn toluene (0.5 mL) at 100 °C for 2 h under nitrogen in the presence of 9 (10 mol %). Conversions and Z:E ratios were determined by analysis of GC-MS.

obtained in medium yields with high selectivities (98:2 for 21 and 22 and 99:1 for 23). In a control reaction, 4c did not give any homocoupled product. Encouraged by these results, the CM reactions of different terminal olefins using 9 as the catalyst were examined, and these results are shown in Table 2 (24− 29). These CM reactions gave medium yields with high ratios of (Z)-olefin products, indicating that catalyst 9 is able to selectively generate (Z)-olefin products without inheriting the original configuration of the substrates. In a RCM reaction of undec-10-en-1-yl undec-10-enoate, the macrocyclic lactone product 30 was obtained in 72% yield with a Z selectivity of 2:1 (Z:E). This reaction required a prolonged reaction time and an elevated temperature, which may have caused the decomposition of 9. The deactivated catalyst could then isomerize the Z product to the E product,8 which would account for the low selectivity of 9 in this RCM reaction.

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CONCLUSION In summary, a 1,2-dicarbadodecaborane(12)-1,2-dithiolate chelating Ru carbene catalyst 9 with high Z selectivity was synthesized. Although the core structure of 9 is similar to those of reported benzene disulfide chelated analogues, the stability and reactivity of 9 is better, which is due to the strongly electron deficient nature and steric bulkiness of the 1,2dicarbadodecaborane(12) ligand. Catalyst 9 can catalyze the cross-metathesis reactions of terminal alkenes with (Z)-but-2ene-1,4-diol and the reactions of other terminal alkenes to give highly Z selective products in moderate to good yields. Catalyst 9 is also able to catalyst a RCM reaction to give a macrocyclic ring compound with a (Z)-olefin structure as the major product. Like other ruthenium-based catalysts, 9 is able to D

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Organometallics 102.2 ppm. 11B NMR (128 MHz, MeOD): δ −3.82, −7.19, −11.53 ppm. IR (KBr): ν 3608, 3539, 2588, 2561, 2060, 1626, 1444, 1305, 1067, 1050, 1006, 972, 944, 889, 727, 516 cm−1. Preparation of Ru-Based Dithiolate Complex 9. In a 2 dram vial charged with a stir bar and sodium 1,2-dicarbadodecaborane(12)1,2-dithiolate (60.5 mg, 0.24 mmol, 1.2 equiv) under an N2 atmosphere was placed a solution of Ru complex 8 (125.2 mg, 0.20 mmol, 1.0 equiv) in tetrahydrofuran (4.0 mL). The resulting mixture was stirred at 22 °C for 3 h, and then the solvent was evaporated under vacuum. Residual tetrahydrofuran was removed through coevaporation with pentane (2 × 4 mL). The resulting solid was dissolved in dichloromethane, passed through a short column of Celite (4 cm in height), placed in a pipet (0.5 cm diameter) with dichloromethane (10 mL). The filtrate is adsorbed onto fresh Celite and subjected to vacuum until complete dryness. The adsorbed material is loaded onto a second short column of Celite (4 cm in height), and washed with Et2O (20 mL), after which the Ru-based complex was collected upon elution with dichloromethane. After removal of solvents and coevaporation with pentane, Ru-based dithiolate complex 9 was isolated as an orange-brown solid (109.8 mg, 0.14 mmol, 72% yield). 1 H NMR (400 MHz, CDCl3): δ 15.55 (s, 1H, Ru = CH), 7.32−7.27 (m, 1H, PhH), 7.12 (d, 3JH,H = 6.1 Hz, 2H, PhH), 7.01 (d, 3JH,H = 8.3 Hz, 1H, PhH), 6.88 (s, 1H, PhH), 6.82 (t, 3JH,H = 7.4 Hz, 1H, PhH), 6.71 (d, 3JH,H = 6.6 Hz, 1H, PhH), 5.95 (s, 1H, PhH), 5.16−5.02 (m, 1H, CH(CH3)2), 3.96 (dd, 3JH,H = 22.1, 10.7 Hz, 2H, N−CH2), 3.73 (t, 3JH,H = 9.8 Hz, 2H, N−CH2), 2.58 (d, 3JH,H = 15.9 Hz, 6H, PhCH3), 2.44 (s, 3H, PhCH3), 2.17 (d, 3JH,H = 4.1 Hz, 6H, PhCH3), 1.69 (d, 3JH,H = 6.7 Hz, 3H, CH3(CHCH3)), 1.64 (s, 3H, PhCH3), 1.44 (d, 3JH,H = 6.6 Hz, 3H, CH3(CHCH3)) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ 259.3, 214.9, 154.5, 141.2, 139.4, 138.3, 136.1, 135.7, 135.1, 134.5, 130.8, 129.9, 129.1, 128.0, 123.8, 122.1, 115.6, 96.9 (C-ocarborane), 86.1, 83.2, 51.8, 51.2, 23.9, 21.2, 21.0, 20.2, 19.1, 18.2, 17.0. 11B NMR (128 MHz, CDCl3): δ −8.31 ppm. 11B{1H} NMR (128 MHz, CDCl3): δ −5.58, −7.55 ppm. 1H{11B} NMR (400 MHz, CDCl3): δ 15.53 (s, 1H, Ru = CH), 7.26 (m, 1H, PhH), 7.09 (d, 3JH,H = 7.8 Hz, 2H, PhH), 6.98 (d, 3JH,H = 8.3 Hz, 1H, PhH), 6.86 (s, 1H, PhH), 6.79 (t, 3JH,H = 7.4 Hz, 1H, PhH), 6.68 (d, 3JH,H = 7.3 Hz, 1H, PhH), 5.93 (s, 1H, PhH), 5.06 (dt, 3JH,H = 13.4, 6.6 Hz, 1H, CH(CH3)2), 3.94 (dd, 3JH,H = 23.7, 10.4 Hz, 2H, N−CH2), 3.74 (d, 3 JH,H = 21.5 Hz, 2H, N−CH2), 2.55 (d, 3JH,H = 14.9 Hz, 6H, PhCH3), 2.41 (s, 3H, PhCH3), 2.15 (d, 3JH,H = 5.8 Hz, 6H, PhCH3), 1.66 (d, 3 JH,H = 6.7 Hz, 3H, CH3(CHCH3)), 1.62 (s, 3H, PhCH3), 1.42 (d, 3 JH,H = 6.5 Hz, 3H, CH3(CHCH3)) ppm. IR (KBr): ν 3446, 3051, 2981, 2919, 2606 (B−H), 2578 (B−H), 2559 (B−H), 1608, 1588, 1575, 1478, 1452, 1427, 1388, 1374, 1308, 1282, 1266, 1185, 1111, 1033, 917, 848, 755, 731, 576, 419 cm−1. HRMS: [M]+ calcd for C33H48B10N2ORuS2, 762.3255; found, 762.3226. Z-Selective Cross-Metathesis (CM) Reactions: General Procedure. An oven-dried 10 mL vial equipped with a magnetic stir bar was charged with alkene substrate (1.0 equiv) and (Z)-2butene-1,4-diol (2.0 equiv)/other alkene substrate (1.0 equiv) in a fume hood. The vial was then sealed, evacuated, and purged with N2. In this vessel was placed a solution of Ru-based complex (5.0 mol %) in tetrahydrofuran (0.5 mL). The resulting solution was stirred for 6 h at 60 °C, after which the reaction mixture was concentrated in vacuo (percent conversion determined by 400 MHz 1H NMR analysis). Purification was performed through silica gel chromatography. The following known compounds were purified by column chromatography, and their spectral data were identical with those reported in the literature: 10,15 brown oil (21.2 mg, yield 75%) in 99:01 Z:E ratio; 13,15 off-white solid (17.8 mg, yield 68%) in 99:01 Z:E ratio; 14,15 pale yellow oil (26.4 mg, yield 80%) in 98:02 Z:E ratio; 15,35 pale yellow oil (19.3 mg, yield 70%) in 97:03 Z:E ratio; 19,15 pale yellow oil (15.9 mg, yield 62%) in 96:04 Z:E ratio; 20,36 pale yellow oil (8.5 mg, yield 50%) in 97:03 Z:E ratio. (Z)-2-((4-Hydroxybut-2-en-1-yl)thio)phenol (11). This was purified by column chromatography to provide a yellow oil (17.9 mg, yield 72%) in 98:02 Z:E ratio. 1H NMR (400 MHz, CDCl3): δ 7.45 (d, 3JH,H = 7.6 Hz, 1H, PhH), 7.27 (t, 3JH,H = 7.5 Hz, 1H, PhH), 6.98 (d, 3JH,H = 8.2 Hz, 1H, PhH), 6.87 (t, 3JH,H = 7.4 Hz, 1H, PhH), 5.83−5.47 (m,

2H, HCCH), 4.24−3.93 (m, 2H, CH2OH and PhOH), 3.72 (d, JH,H = 5.6 Hz, 2H, (CHCH)CH2(OH)), 3.36 (d, 3JH,H = 7.0 Hz, 2H, SCH2(CHCH)) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ 158.0, 136.7, 132.1, 131.6, 126.6, 120.3, 117.9, 115.2, 57.6, 32.9 ppm. ESI-MS: [M + Na]+ calcd for C10H12O2S, 196.2640; found, 219.0448. Anal. Found (calcd) for C10H12O2S: C, 61.20 (61.15); H, 6.16 (6.22). (Z)-2-((5-Hydroxypent-3-en-1-yl)oxy)benzaldehyde (12). This was purified by column chromatography to provide a colorless oil (21.2 mg, yield 83%) in 99:01 Z:E ratio. 1H NMR (400 MHz, CDCl3): δ 10.44 (s, 1H, PhCHO), 7.82 (d, 3JH,H = 7.6 Hz, 1H, PhH), 7.54 (t, 3 JH,H = 7.8 Hz, 1H, PhH), 7.03 (t, 3JH,H = 7.4 Hz, 1H, PhH), 6.97 (d, 3 JH,H = 8.4 Hz, 1H, PhH), 5.91−5.74 (m, 1H, CH(CH2OH)), 5.66 (dd, 3JH,H = 17.7, 7.9 Hz, 1H, (PhOCH2CH2)CH), 4.27 (d, 3JH,H = 6.2 Hz, 2H, (CHCH)CH2(OH)), 4.12 (t, 3JH,H = 6.3 Hz, 2H, (CH = CHCH2)CH2), 2.67 (dd, 3JH,H = 13.3, 6.6 Hz, 2H, (PhOCH2)CH2), 1.86 (s, 1H, (CH = CHCH2)OH) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ 190.0, 161.0, 136.0, 131.5, 128.9, 127.6, 124.8, 120.8, 112.5, 67.7, 58.5, 27.5 ppm. ESI-MS: [M + Na]+ calcd for C12H14O3, 206.2410; found, 229.0835. Anal. Found (calcd) for C12H14O3: C, 69.89 (69.96); H, 6.84 (6.87). (Z)-12-Hydroxydodec-10-en-1-yl Benzoate (16). This was purified by column chromatography to provide a pale yellow oil (32.1 mg, yield 83%) in 98:02 Z:E ratio. 1H NMR (400 MHz, CDCl3): δ 8.05 (d, 3JH,H = 7.8 Hz, 2H, PhH), 7.55 (t, 3JH,H = 7.3 Hz, 1H, PhH), 7.44 (t, 3JH,H = 7.5 Hz, 2H, PhH), 5.66−5.56 (m, 1H, CH(CH2)OH), 5.56−5.44 (m, 1H, (CH2CH2CH2)CH), 4.31 (t, 3JH,H = 6.6 Hz, 2H, PhCOOCH2), 4.19 (t, 3JH,H = 5.1 Hz, 2H, CH2(OH)), 2.06 (dd, 3JH,H = 13.7, 6.8 Hz, 2H, (CH = CHCH2)CH2), 1.81−1.72 (m, 2H, (PhCOOCH2)CH2), 1.54 (s, 1H, (CHCHCH2)OH), 1.49−1.40 (m, 2H, (CH = CHCH2CH2)CH2), 1.35 (m, 4H), 1.29 (s, 6H) ppm; 13C{1H} NMR (150 MHz, CDCl3) δ 133.2, 132.8, 130.5, 129.5, 128.3, 65.1, 58.6, 29.7, 29.5, 29.4, 29.3, 29.2, 29.1, 28.7, 27.4, 26.0 ppm. ESI-MS: [M + Na]+ calcd for C19H28O3, 304.4220; found, 327.1937. Anal. Found (calcd) for C19H28O3: C, 74.96 (74.83); H, 9.27 (9.21). (Z)-7-Hydroxyhept-5-en-1-yl Benzoate (17). This was purified by column chromatography to provide a pale yellow oil (22.3 mg, yield 72%) in 98:02 Z:E ratio. 1H NMR (600 MHz, CDCl3): δ 8.04 (d, 3JH,H = 7.7 Hz, 1H, PhH), 7.56 (t, 3JH,H = 7.4 Hz, 1H, PhH), 7.44 (t, 3JH,H = 7.7 Hz, 1H, PhH), 5.68−5.60 (m, 1H, (CH2OH)CH), 5.59−5.51 (m, 1H, (PhCOO(CH2)4)CH), 4.33 (t, 3JH,H = 6.6 Hz, 1H, PhCOOCH2), 4.21 (d, 3JH,H = 6.6 Hz, 1H, CH2(OH)), 2.17 (q, 3JH,H = 7.3 Hz, 1H, (HOCH2CHCH)CH2), 1.81−1.76 (m, 1H, (PhCOOCH2)CH2), 1.67 (s, 1H, (CHCHCH2)OH), 1.54 (dt, 3JH,H = 15.0, 7.5 Hz, 1H, (PhCOOCH2CH2)CH2) ppm. 13C{1H} NMR (150 MHz, CDCl3): δ 166.7, 132.9, 132.3, 130.3, 129.5, 129.0, 128.3, 64.7, 58.5, 28.21, 26.9, 25.9 ppm. ESI-MS: [M + Na]+ calcd for C14H18O3, 234.2950; found, 257.1154. Anal. Found (calcd) for C14H18O3: C, 71.77 (71.62); H, 7.74 (7.88). (Z)-4-((4-Nitrophenyl)amino)but-2-en-1-ol (18). This was purified by column chromatography to provide a pale yellow oil (20.4 mg, yield 77%) in 99:01 Z:E ratio. 1H NMR (400 MHz, CDCl3): δ 8.09 (d, 3JH,H = 7.8 Hz, 2H, PhH), 6.55 (d, 3JH,H = 8.0 Hz, 2H, PhH), 5.95−5.79 (m, 1H, (HOCH2)CH), 5.79−5.56 (m, 1H, (PhNHCH2)CH), 4.66 (s, 1H, PhNH), 4.32 (d, 3JH,H = 5.4 Hz, 2H, (PhNH)CH2), 3.93 (t, 3JH,H = 5.9 Hz, 2H, CH2(OH)), 1.65 (s, 1H, (CHCHCH2)OH) ppm. 13 C{1H} NMR (100 MHz, CDCl3): δ 153.0, 138.0, 132.4, 127.7, 126.4, 111.2, 58.5, 40.5 ppm. ESI-MS: [M + Na]+ calcd for C10H12N2O3: 208.1270, found: 231.0741. Anal. Found (calcd) for C10H12N2O3: C, 57.69 (57.72); H, 5.81 (5.75); N, 13.45 (13.35). (Z)-Dec-5-ene-1,10-diyl Dibenzoate (21). This was purified by column chromatography to provide a pale yellow oil (14.7 mg, yield 61%) in 98:02 Z:E ratio. 1H NMR (400 MHz, CDCl3): δ 8.04 (dd, 3 JH,H = 8.3, 1.2 Hz, 4H, PhH), 7.55 (t, 3JH,H = 7.4 Hz, 2H, PhH), 7.43 (t, 3JH,H = 7.6 Hz, 4H, PhH), 5.43 (ddd, 3JH,H = 14.5, 6.5, 3.3 Hz, 2H, CHCH), 4.32 (t, 3JH,H = 6.6 Hz, 4H, PhCOOCH2), 2.12 (dd, 3JH,H = 11.8, 6.3 Hz, 4H, (CHCH)CH2), 1.77 (ddd, 3JH,H = 9.6, 6.8, 3.3 Hz, 4H, (PhCOOCH2)CH2), 1.53 (dd, 3JH,H = 15.1, 7.8 Hz, 4H, (PhCOOCH2CH2)CH2) ppm. 13C{1H} NMR (150 MHz, CDCl3): δ 132.8, 130.3, 129.8, 129.5, 128.3, 64.9, 28.3, 28.2, 26.8, 26.1 ppm. ESI3

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DOI: 10.1021/acs.organomet.7b00556 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics MS: [M + Na]+ calcd for C24H28O4, 380.4840; found, 403.1882. Anal. Found (calcd) for C24H28O4: C, 75.76 (75.71); H, 7.42 (7.39). (Z)-2,2′-(Dec-5-ene-1,10-diyl)bis(isoindoline-1,3-dione) (22). This was purified by column chromatography to provide a brown oil (18.0 mg, yield 66%) in 98:02 Z:E ratio. 1H NMR (400 MHz, CDCl3): δ 7.85 (dd, 3JH,H = 5.4, 3.0 Hz, 4H, PhH), 7.72 (dd, 3JH,H = 5.4, 3.0 Hz, 4H, PhH), 5.37 (dt, 3JH,H = 9.4, 4.2 Hz, 2H), 3.69 (td, 3JH,H = 7.3, 2.7 Hz, 4H, (C8H4NO2)CH2), 2.08 (dd, 3JH,H = 12.7, 7.2 Hz, 4H, (CH CH)CH2), 1.69 (dd, 3JH,H = 15.1, 7.5 Hz, 4H, (C8H4NO2CH2)CH2), 1.41 (dt, 3JH,H = 15.1, 7.5 Hz, 4H, (CH = CHCH2)CH2) ppm. 13 C{1H} NMR (150 MHz, CDCl3): δ 168.4, 133.8, 132.1, 130.2, 129.6, 123.1, 37.9, 32.0, 28.1, 26.8, 26.7 ppm. ESI-MS: [M + Na]+ calcd for C26H26N2O4, 430.5040; found, 453.1781. Anal. Found (calcd) for C26H26N2O4 :C, 72.54 (72.66); H, 6.09 (6.13); N, 6.51 (6.44). (Z)-1,6-Bis(4-nitrophenoxy)hex-3-ene (23). This was purified by column chromatography to provide a brown oil (16.2 mg, yield 71%) in 99:01 Z:E ratio. 1H NMR (400 MHz, CDCl3): δ 8.22 (d, 3JH,H = 9.2 Hz, 4H, PhH), 6.96 (d, 3JH,H = 9.2 Hz, 4H, PhH), 5.69 (t, 3JH,H = 4.8 Hz, 2H, CHCH), 4.12 (t, 3JH,H = 6.5 Hz, 4H, PhOCH2), 2.67 (dd, 3 JH,H = 12.0, 6.3 Hz, 4H, (PhOCH2)CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ 163.8, 141.5, 127.5, 125.9, 114.4, 68.0, 27.3 ppm. ESI-MS: [M + Na]+ calcd for C18H18N2O6, 358.3500; found, 381.1056. Anal. Found (calcd) for C18H18N2O6: C, 60.33 (60.18); H, 5.06 (5.13); N, 7.82 (7.68). (Z)-Dodec-2-ene-1,12-diyl Dibenzoate (24). This was purified by column chromatography to provide a brown oil (32.8 mg, yield 63%) in 93:07 Z:E ratio. 1H NMR (600 MHz, CDCl3): δ 8.05 (d, 3JH,H = 2.9 Hz, 2H, PhH), 8.04 (d, 3JH,H = 1.7 Hz, 2H, PhH), 7.55 (t, 3JH,H = 6.8 Hz, 2H, PhH), 7.44 (td, 3JH,H = 7.8, 4.1 Hz, 4H, PhH), 5.78−5.57 (m, 2H), 4.87 (d, 3JH,H = 6.2 Hz, 2H, PhCOOCH2(CHCH)), 4.31 (t, 3 JH,H = 6.7 Hz, 2H, PhCOOCH2), 2.16 (q, 3JH,H = 7.1 Hz, 2H, (PhCOOCH 2 )CH 2 ), 1.76 (dd, 3 J H,H = 13.0, 5.9 Hz, 2H, (PhCOOCH2CH2)CH2), 1.40 (d, 3JH,H = 6.6 Hz, 2H, (PhCOO(CH2)3)CH2), 1.33 (d, 3JH,H = 4.8 Hz, 2H, (PhCOO(CH2)4)CH2 and (PhCOO(CH2)5)CH2), 1.30 (s, 6H) ppm. 13C{1H} NMR (150 MHz, CDCl3): δ 166.7, 166.6, 135.7, 132.9, 132.8, 130.5, 129.6, 129.5, 128.3, 123.3, 113.3, 99.9, 65.1, 60.9, 29.4, 29.2, 29.1, 28.7, 27.6, 26.0 ppm. ESI-MS: [M + Na]+ calcd for C26H32O4, 408.5380; found, 431.2195. Anal. Found (calcd) for C26H32O4: C, 76.44 (76.28); H, 7.90 (7.79). (Z)-8-(4-Nitrophenoxy)oct-5-en-1-yl Benzoate (25). This was purified by column chromatography to provide a brown oil (30.2 mg, yield 59%) in 94:06 Z:E ratio. 1H NMR (600 MHz, CDCl3): δ 8.18 (dd, 3JH,H = 9.4, 3.4 Hz, 2H, PhH), 8.04 (d, 3JH,H = 7.4 Hz, 2H, PhH), 7.56 (t, 3JH,H = 7.4 Hz, 2H, PhH), 7.44 (t, 3JH,H = 7.7 Hz, 2H, PhH), 6.93 (d, 3JH,H = 9.2 Hz, 2H, PhH), 5.58 (dd, 3JH,H = 16.8, 8.3 Hz, 1H (p-NO2PhOCH2CH2)CH), 5.49 (dd, 3JH,H = 18.0, 7.2 Hz, 1H, PhCOO(CH 2 ) 4 )CH), 4.34 (dd, 3 J H,H = 12.1, 5.6 Hz, 2H, PhCOOCH2), 4.05 (t, 3JH,H = 6.6 Hz, 2H, p-NO2PhOCH2), 2.59 (q, 3JH,H = 6.9 Hz, 2H, (p-NO2PhOCH2)CH2), 2.18 (q, 3JH,H = 7.3 Hz, 2H, (PhCOOCH2CH2CH2)CH2), 1.81 (dd, 3JH,H = 15.0, 7.0 Hz, 2H, (PhCOOCH2)CH2), 1.57 (dd, 3JH,H = 15.3 Hz, 7.6 Hz, 2H, (PhCOOCH2CH2)CH2) ppm. 13C{1H} NMR (150 MHz, CDCl3): δ 166.6, 163.9, 136.3, 132.9, 132.5, 129.5, 128.3, 125.9, 124.7, 123.8, 114.4, 68.2, 64.8, 28.3, 27.2, 26.9, 25.9 ppm. ESI-MS: [M + Na]+ calcd for C21H23NO5, 369.4170; found, 392.1468. Anal. Found (calcd) for C21H23NO5: C, 68.28 (68.32); H, 6.28 (6.26); N, 3.79 (3.70). (Z)-13-(4-Nitrophenoxy)tridec-10-en-1-yl Benzoate (26). This was purified by column chromatography to provide a brown oil (31.2 mg, yield 56%) in 95:05 Z:E ratio. 1H NMR (600 MHz, CDCl3): δ 8.20 (d, 3 JH,H = 9.2 Hz, 2H, PhH), 8.05 (d, 3JH,H = 7.5 Hz, 2H, PhH), 7.56 (t, 3 JH,H = 7.4 Hz, 1H, PhH), 7.44 (t, 3JH,H = 7.7 Hz, 2H, PhH), 6.94 (d, 3 JH,H = 9.2 Hz, 2H, PhH), 5.56 (dd, 3JH,H = 17.9, 7.5 Hz, 1H, (pNO2PhOCH2CH2)CH), 5.51−5.38 (m, 1H, (PhCOO(CH2)9)CH), 4.31 (t, 3JH,H = 6.7 Hz, 2H, PhCOOCH2), 4.05 (t, 3JH,H = 6.8 Hz, 2H, p-NO2PhOCH2), 2.58 (dd, 3JH,H = 13.8, 7.0 Hz, 2H, (PhCOOCH2)CH2), 2.07 (dt, 3JH,H = 11.5, 5.7 Hz, 2H, (p-NO2PhOCH2)CH2), 1.76 (dd, 3JH,H = 14.5, 7.1 Hz, 2H, (PhCOO(CH2)8)CH2), 1.43 (dd, 3JH,H = 12.0, 7.0 Hz, 2H, (PhCOOCH2CH2)CH2), 1.36 (d, 3JH,H = 5.9 Hz,

4H, (PhCOO(CH2)7)CH2 and (PhCOOCH2CH2CH2)CH2), 1.30 (s, 6H) ppm. 13C{1H} NMR (150 MHz, CDCl3): δ 166.7, 164.0, 133.4, 132.8, 131.6, 130.4, 129.5, 128.3, 125.9, 123.8, 114.4, 68.3, 65.1, 29.7, 29.5, 29.5, 29.4, 29.2, 28.7, 27.4, 27.1, 26.0 ppm. ESI-MS: [M + Na]+ calcd for C26H33NO5, 439.5520; found, 462.2247. Anal. Found (calcd) for C26H33NO5: C, 71.05 (70.93); H, 7.57 (7.51); N, 3.19 (3.03). (Z)-2-(8-(4-Nitrophenoxy)oct-5-en-1-yl)isoindoline-1,3-dione (27). This was purified by column chromatography to provide a brown oil (27.5 mg, yield 55%) in 96:04 Z:E ratio. 1H NMR (600 MHz, CDCl3): δ 8.17 (dd, 3JH,H = 9.4, 2.7 Hz, 2H, PhH), 7.84 (dd, 3JH,H = 5.3, 3.1 Hz, 2H, PhH), 7.71 (dd, 3JH,H = 5.4, 3.0 Hz, 2H, PhH), 6.93 (dd, 3JH,H = 9.2, 2.1 Hz, 2H, PhH), 5.58−5.50 (m, 1H, (pNO2PhOCH2CH2)CH), 5.46 (dt, 3JH,H = 10.9, 8.0 Hz, 1H, (C8H4NO2(CH2)4)CH), 4.04 (t, 3JH,H = 6.7 Hz, 2H, p-NO2PhOCH2), 3.70 (t, 3JH,H = 7.3 Hz, 2H, (C8H4NO2)CH2), 2.58 (q, 3JH,H = 6.8 Hz, 2H, (p-NO 2 PhOCH 2 )CH 2 ), 2.15 (q, 3 J H,H = 7.3 Hz, 2H, (C8H4NO2(CH2)3)CH2), 1.72 (dd, 3JH,H = 15.1, 7.6 Hz, 2H, (C8H4NO2CH2)CH2)), 1.44 (dd, 3JH,H = 13.8, 6.0 Hz, 2H, (C 8 H 4 NO 2 CH 2 CH 2 )CH 2 ) ppm. 13 C{ 1 H} NMR (150 MHz, CDCl3): δ 168.4, 164.0, 133.9, 133.1, 132.5, 132.1, 125.9, 124.6, 123.2, 114.4, 68.2, 37.8, 28.1, 27.1, 26.8, 26.6 ppm. ESI-MS: [M + Na]+ calcd for C22H22N2O5, 394.4270; found, 417.1411. Anal. Found (calcd) for C22H22N2O5: C, 66.99 (66.85); H, 5.62 (5.55); N, 7.10 (7.01). (Z)-7-(1,3-Dioxoisoindolin-2-yl)hept-2-en-1-yl Benzoate (28). This was purified by column chromatography to provide a brown oil (26.4 mg, yield 57%) in 93:07 Z:E ratio. 1H NMR (400 MHz, CDCl3): δ 8.06 (d, 3JH,H = 7.3 Hz, 2H, PhH), 7.85 (dd, 3JH,H = 5.3, 3.1 Hz, 2H, PhH), 7.72 (dd, 3JH,H = 5.3, 3.1 Hz, 2H, PhH), 7.56 (t, 3JH,H = 7.4 Hz, 1H, PhH), 7.44 (t, 3JH,H = 7.6 Hz, 2H, PhH), 5.90−5.77 (m, 1H, (PhCOOCH2)CH), 5.76−5.62 (m, 1H, (C8H4NO2(CH2)4)CH), 4.77 (d, 3JH,H = 6.2 Hz, 2H, PhCOOCH2), 3.70 (d, 3JH,H = 7.2 Hz, 2H, C8H4NO2CH2), 2.16 (q, 3JH,H = 7.1 Hz, 2H, (C8H4NO2(CH2)3)CH2), 1.71 (dd, 3JH,H = 15.2, 7.5 Hz, 2H, (C8H4NO2CH2)CH2), 1.48 (dd, 3 JH,H = 15.1, 7.4 Hz, 2H, (C8H4NO2CH2CH2)CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ 168.4, 166.5, 135.5, 134.7, 133.8, 132.8, 132.1, 130.3, 129.6, 128.3, 124.5, 124.0, 123.2, 60.7, 37.7, 28.1, 27.1, 26.5 ppm. ESI-MS: [M + Na]+ calcd for C22H21NO4, 363.4130; found, 386.1363. Anal. Found (calcd) for C22H21NO4: C, 72.71 (72.64); H, 5.82 (5.69); N, 3.85 (3.78). (Z)-5-(4-Nitrophenoxy)pent-2-en-1-yl Benzoate (29). This was purified by column chromatography to provide a brown oil (25.5 mg, yield 62%) in 96:04 Z:E ratio. 1H NMR (600 MHz, CDCl3): δ 8.19 (d, 3 JH,H = 9.2 Hz, 2H, PhH), 8.05 (d, 3JH,H = 7.4 Hz, 2H, PhH), 7.57 (t, 3 JH,H = 7.4 Hz, 1H, PhH), 7.45 (t, 3JH,H = 7.7 Hz, 2H, PhH), 6.95 (t, 3 JH,H = 6.4 Hz, 2H, PhH), 5.90−5.84 (m, 1H, (PhCOOCH2)CH), 5.84−5.75 (m, 1H, (p-NO2PhOCH2CH2)CH), 4.94 (d, 3JH,H = 6.7 Hz, 2H, PhCOOCH2), 4.12 (t, 3JH,H = 6.5 Hz, 2H, p-NO2PhOCH2), 2.74 (d, 3JH,H = 6.7 Hz, 2H, (p-NO2PhOCH2)CH2) ppm. 13C{1H} NMR (150 MHz, CDCl3): δ 166.4, 163.8, 137.8, 133.1, 130.0, 129.8, 129.6, 128.4, 126.7, 125.9, 114.4, 67.7, 60.6, 27.5 ppm. ESI-MS: [M + Na]+ calcd for C18H17NO5, 327.3360; found, 350.0999. Anal. Found (calcd) for C18H17NO5: C, 66.05 (66.13); H, 5.23 (5.28); N, 4.28 (4.22). RCM Reactions of 30: (Z)-Oxacyclohenicos-11-en-2-one (30). Following the general procedure, a solution of Ru-based complex (9.6 mg, 12.6 μmol, 10.0 mol %) in toluene (0.5 mL) was transferred by syringe to a vial charged with 10-undecenoic acid 10-undecen-1-yl ester (42.7 mg, 0.127 mmol, 1.0 equiv). The resulting solution was stirred for 12 h at 100 °C. Analysis of the unpurified mixture by GCMS37 found a 2:1 Z:E ratio.

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DOI: 10.1021/acs.organomet.7b00556 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics

(11) (a) Cannon, J. S.; Zou, L.; Liu, P.; Lan, Y.; O’Leary, D. J.; Houk, K. N.; Grubbs, R. H. J. Am. Chem. Soc. 2014, 136, 6733. (b) Rosebrugh, L. E.; Marx, V. M.; Keitz, B. K.; Grubbs, R. H. J. Am. Chem. Soc. 2013, 135, 10032. (12) (a) Cannon, J. S.; Grubbs, R. H. Angew. Chem., Int. Ed. 2013, 52, 9001. (b) Dornan, P. K.; Wickens, Z. K.; Grubbs, R. H. Angew. Chem., Int. Ed. 2015, 54, 7134. (c) Herbert, M. B.; Grubbs, R. H. Angew. Chem., Int. Ed. 2015, 54, 5018. (13) Keitz, B. K.; Endo, K.; Herbert, M. B.; Grubbs, R. H. J. Am. Chem. Soc. 2011, 133 (25), 9686. (14) Khan, R. K. M.; Torker, S.; Hoveyda, A. H. J. Am. Chem. Soc. 2013, 135, 10258. (15) Koh, M. J.; Khan, R. K. M.; Torker, S.; Yu, M.; Mikus, M. S.; Hoveyda, A. H. Nature 2015, 517, 181. (16) (a) Khan, R. K. M.; Torker, S.; Hoveyda, A. H. J. Am. Chem. Soc. 2014, 136, 14337. (b) McKinty, A. M.; Lund, C.; Stephan, D. W. Organometallics 2013, 32, 4730. (c) McKinty, A. M.; Stephan, D. W. Dalton Trans. 2014, 43, 2710. (d) McKinty, A. M.; Stephan, D. W. Dalton Trans. 2016, 45, 3844. (17) Mikus, M. S.; Torker, S.; Xu, C.; Li, B.; Hoveyda, A. H. Organometallics 2016, 35, 3878. (18) (a) Rosen, E. L.; Sung, D. H.; Chen, Z.; Lynch, V. M.; Bielawski, C. W. Organometallics 2010, 29, 250. (b) Teo, P.; Grubbs, R. H. Organometallics 2010, 29, 6045. (c) Koh, M. J. R.; Khan, K. M.; Torker, S.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2014, 53, 1968. (19) (a) Scholz, M.; Hey-Hawkins, E. Chem. Rev. 2011, 111 (11), 7035. (b) Bregadze, V. I. Chem. Rev. 1992, 92, 209. (c) Issa, F.; Kassiou, M.; Rendina, L. M. Chem. Rev. 2011, 111 (9), 5701. (20) (a) Williams, R. E. Chem. Rev. 1992, 92, 177. (b) Spokoyny, A. M.; Machan, C. W.; Clingerman, D. J.; Rosen, M. S.; Wiester, M. J.; Kennedy, R. D.; Stern, C. L.; Sarjeant, A. A.; Mirkin, C. A. Nat. Chem. 2011, 3, 590. (21) Tsuboya, N.; Lamrani, M.; Hamasaki, R.; Ito, M.; Mitsuishi, M.; Miyashita, T.; Yamamoto, Y. J. Mater. Chem. 2002, 12, 2701. (22) Zheng, G. X.; Jones, J. R. M. J. Am. Chem. Soc. 1983, 105, 6487. (23) (a) Lavallo, V.; Wright, J. H., II; Tham, F. S.; Quinlivan, S. Angew. Chem., Int. Ed. 2013, 52, 3172. (b) Joost, M.; Estévez, L.; Miqueu, K.; Amgoune, A.; Bourissou, D. Angew. Chem., Int. Ed. 2015, 54, 5236. (c) Messina, M. S.; Axtell, J. C.; Wang, Y.; Chong, P.; Wixtrom, A. I.; Kirlikovali, K. O.; Upton, B. M.; Hunter, B. M.; Shafaat, O. S.; Khan, S. I.; Winkler, J. R.; Gray, H. B.; Alexandrova, A. N.; Maynard, H. D.; Spokoyny, A. M. J. Am. Chem. Soc. 2016, 138, 6952. (d) Eleazer, B. J.; Smith, M. D.; Popov, A. A.; Peryshkov, D. V. Chem. Sci. 2017, 8, 5399. (24) Ireland, B. J.; Dobigny, B. T.; Fogg, D. E. ACS Catal. 2015, 5 (8), 4690. (25) Shoji, Y.; Ishige, R.; Higashihara, T.; Watanabe, J.; Ueda, M. Macromolecules 2010, 43, 805. (26) Kitagawa, T.; Nishino, J.; Inomata, T.; Ozawa, T.; Funahashi, Y.; Masuda, H. Chem. Commun. 2016, 52, 4780. (27) Zhang, F.; Wang, X. H.; Ma, J. J.; Gong, P. Eur. J. Med. Chem. 2011, 21, 352. (28) Dai, H. M.; Yu, C.; Lu, C. S.; Yan, H. Eur. J. Org. Chem. 2016, 2016, 1255. (29) Yu, W.; Xu, X. H.; Qing, F. L. Adv. Synth. Catal. 2015, 357, 2039. (30) Danilov, L. L.; Balagurova, N. M.; Vinnikova, A. N.; Utkina, N. S.; Torgov, V. I.; Kalinchuk, N. A.; Druzhinina, T. N.; Veselovsky, V. V. Russ. J. Bioorg. Chem. 2014, 40, 89. (31) Popescu, A. R.; Musteti, A. D.; Ferrer-Ugalde, A.; Vinas, C.; Nunez, R.; Teixidor, F. Chem. - Eur. J. 2012, 18, 3174. (32) Thoumazet, C.; Grutzmacher, H.; Deschamps, B.; Ricard, L.; le Floch, P. Eur. J. Inorg. Chem. 2006, 2006, 3911. (33) Hartsel, J. A.; Wong, D. M.; Mutunga, J. M.; Ma, M.; Anderson, T. D.; Wysinski, A.; Islam, R.; Wong, E. A.; Paulson, S. L.; Li, J. Y.; Lam, P. C. H. Bioorg. Med. Chem. Lett. 2012, 22, 4593. (34) Ciardiello, J. J.; Galloway, W. R. J. D.; O’Connor, C. J.; Sore, H. F.; Stokes, J. E.; Wu, Y. T.; Spring, D. R. Tetrahedron 2016, 72, 3567.

Crystal structure for complex 9 and NMR spectra for compounds and complexes synthesized (PDF) Accession Codes

CCDC 1504008 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_ [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail for J.W.: [email protected]. *E-mail for G.L.: [email protected]. ORCID

Tao Wang: 0000-0003-2675-7039 Xiaobo Yu: 0000-0002-0168-1165 Jianhui Wang: 0000-0003-2581-7247 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Grant Nos. 21572155 and 21372175) and the Natural Science Foundation of Tianjin (No. 16JCYBJC19700).

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REFERENCES

(1) (a) Vougioukalakis, G. C.; Grubbs, R. H. Chem. Rev. 2010, 110, 1746. (b) Schrock, R. R. Chem. Rev. 2009, 109, 3211. (c) Quigley, B. L.; Grubbs, R. H. Chem. Sci. 2014, 5, 501. (d) Johansson Seechurn, C. C. C.; Kitching, M. O.; Colacot, T. J.; Sniekus, V. Angew. Chem., Int. Ed. 2012, 51, 5062. (2) (a) Nussbaumer, P.; Ettmayer, P.; Carsten, P.; Rosenbeiger, D.; Hogenauer, K. Chem. Commun. 2005, 5086. (b) Biswas, K.; Lin, H.; Njardarson, J. T.; Chappell, M. D.; Chou, T. C.; Guan, Y. B.; Tong, W. P.; He, L. F.; Horwitz, S. B.; Danishefsky, S. J. J. Am. Chem. Soc. 2002, 124, 9825. (3) (a) Boydston, A. J.; Holcombe, T. W.; Unruh, D. A.; Fréchet, J. M. J.; Grubbs, R. H. J. Am. Chem. Soc. 2009, 131 (15), 5388. (b) Bielawski, C. W.; Benitz, D.; Grubbs, R. H. Science 2002, 297, 2041. (4) (a) Handbook of Metathesis; Grubbs, R. H., Ed.; Wiley-VCH: Weinheim, Germany, 2003. (b) Garber, B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 8168. (c) Kong, J.; Chen, C. Y.; Balsells-Padros, J.; Cao, Y.; Dunn, R. F.; Dolman, S. J.; Janey, J.; Li, H.; Zacuto, M. J. J. Org. Chem. 2012, 77, 3820. (5) (a) Akiyama, T.; Takada, K.; Oikawa, T.; Matsuura, N.; Ise, Y.; Okada, S.; Matsunaga, S. Tetrahedron 2013, 69, 6560. (b) Nunnery, J. K.; Engene, N.; Byrum, T.; Cao, Z.; Jabba, S. V.; Pereira, A. R.; Matainaho, T.; Murray, T. F.; Gerwick, W. H. J. Org. Chem. 2012, 77, 4198. (6) Ibrahem, I.; Yu, M.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2009, 131, 3844. (7) (a) Zhang, H.; Yu, E. C.; Torker, S.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2014, 136, 16493. (b) Meek, S. J.; O'Brien, R. V.; Llaveria, J.; Schrock, R. R.; Hoveyda, A. H. Nature 2011, 471, 461. (8) (a) Speed, A. W. H.; Mann, T. J.; O’Brien, R. V.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2014, 136, 16136. (b) Yu, M.; Wang, C. B.; Kyle, A. F.; Jakubec, P.; Dixon, D. J.; Schrock, R. R.; Hoveyda, A. H. Nature 2011, 479, 88. (c) Cain, M. F.; Forrest, W. P.; Peryshkov, D. V.; Schrock, R. R.; Müller, P. J. Am. Chem. Soc. 2013, 135, 15338. (9) Endo, K.; Grubbs, R. H. J. Am. Chem. Soc. 2011, 133 (22), 8525. (10) Keitz, B. K.; Endo, K.; Patel, P. R.; Herbert, M. B.; Grubbs, R. H. J. Am. Chem. Soc. 2012, 134, 693. G

DOI: 10.1021/acs.organomet.7b00556 Organometallics XXXX, XXX, XXX−XXX

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Organometallics (35) Rani, S.; Babu, J. L.; Vankar, Y. D. Synth. Commun. 2003, 33, 4043. (36) Singh, K.; Staig, S. J.; Weaver, J. D. J. Am. Chem. Soc. 2014, 136, 5275. (37) Fürstner, A.; Langemann, K. Synthesis 1997, 1997, 792.

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DOI: 10.1021/acs.organomet.7b00556 Organometallics XXXX, XXX, XXX−XXX