Direct Conversion of Ethyl Ketone to Alkyl Ketone via Chelation

DOI: 10.1021/acs.organomet.8b00309. Publication Date (Web): July 10, 2018. Copyright © 2018 American Chemical Society. *E-mail for J.W.: [email protected]...
3 downloads 0 Views 612KB Size
Download PDF
Article Cite This: Organometallics XXXX, XXX, XXX−XXX

Direct Conversion of Ethyl Ketone to Alkyl Ketone via ChelationAssisted Rhodium(I)-Catalyzed Carbon−Carbon Bond Cleavage: Ligands Play an Important Role in the Inhibition of β‑Hydrogen Elimination Shutao Wu,†,‡ Siyuan Luo,†,‡ Weijie Guo,†,‡ Tao Wang,†,‡ Qingxiao Xie,†,‡ Jianhui Wang,*,†,‡ and Guiyan Liu*,§ Downloaded via UNIV OF SOUTH DAKOTA on July 11, 2018 at 04:11:54 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

†

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: Quinolinone derivatives were synthesized by exchanging the ethyl group of 1-(quinolin-8-yl)propan-1-one with substituted styrenes via group-directed carbon−carbon bond cleavage. A series of substituted styrenes were reacted with 1-(quinolin-8-yl)propan-1-one for the production of various substituted 3-phenyl-1-(quinolin-8-yl)propan-1-ones in medium and good yields. The catalytic system combining [Rh(COD)Cl]2 (5.0 mol %) with Et3N (2.5 equiv) and 1,3bis(diphenylphosphino)propane (10 mol %) was optimal for these transformations.

■

INTRODUCTION Obtaining useful complex molecules via the rapid transformation of readily available feedstocks has been a continuous endeavor in synthetic organic chemistry. Cleavage of carbon− carbon (C−C) bonds mediated by transition metals is essential in the rapid formation of novel compounds through nontraditional retrosynthetic disconnections.1−3 Intermediates generated by metal-mediated C−C bond activations are also used as important synthons in many transformations.2 Therefore, developing an efficient synthetic method based on C−C activation has received considerable attention.3 However, C−C bonds are not easily activated because they are kinetically and thermodynamically stable.2e,g Normally, a C−C bond cleavage reaction is achieved by releasing ring tension for the formation of a stable metal complex2a,e−g,m or generation of an aromatic compound2c,e,k and overcoming activation barriers. Assisted chelation2c−f,h−j is another useful strategy for promoting the C−C activation of nontensile molecules. In the past years, many elegant works have been developed on the basis of chelation-assisted C−C activation strategies. For example, Murai4 reported decarbonylative cleavage of the C−C bond of alkyl phenyl ketones in the presence of Ru3(CO)12 in 1999. The chelation of nitrogen to Ru is the key feature in the formation of a metallacycle during C−C bond cleavage. Jun demonstrated the facile catalytic C−C bond activation of unstrained ketone through the assisted chelation of 2-amino-3picoline by a soluble rhodium(I) complex.5 Douglas reported the intermolecular carboacylation of an olefin through the activation of an unstrained C−C bond6 and the intramolecular © XXXX American Chemical Society

alkene carboacylation reaction initiated by quinolone directed rhodium-catalyzed C−C bond activation.7 Johnson indicated that C−C bond activation is the rate-limiting step for species with minimal alkene substitution in the transformations, whereas alkene insertion is rate limiting for sterically encumbered substrates.8 Dong developed a regioselective3b or an enantioselective 9 carboacylation of olefins and benzocyclobutenones for accessing fused-ring compounds, an intramolecular alkyne insertion reaction of benzocyclobutenones,10 a decarbonylative coupling of isatins with alkynes11 or isocyanates,12 an enantioselective carboacylation of oximes (imines) via group-directed rhodium-catalyzed C−C activation,13 and the synthesis of functionalized α-tetralones via catalytic activation of C−C bonds in cyclopentanones or cyclohexanones.14 Shi developed an efficient rhodium(I)catalyzed decarbonylation through double C−C cleavage with the assistance of an N-containing directing group, providing an alternative method for synthesizing biaryls and alkenyl and alkyl benzenes.15 Our group reported a chelationassisted coupling reaction via C−C activation, which allows the direct exchange of the alkyl group with the aryl group.16 In 2018, Dong determined that Co2(CO)8/P[3,5-(CF3)2C6H3]3 is an effective metal/ligand combination that exhibits catalytic activity similar to that of C−C bond cleavage with rhodium catalysts.17 In a previous study, Suggs and Jun reported that 8quinolinyl alkyl ketone containing β-hydrogens react with Received: May 12, 2018

A

DOI: 10.1021/acs.organomet.8b00309 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics ethylene to yield 8-quinolinyl ethyl ketone in the presence of Rh(I) or Ir(I) complexes (Scheme 1, path a).18 In contrast,

Table 1. Optimization of the Reaction Conditions for the Direct Conversion of Ethyl Ketone to Alkyl Ketonea

Scheme 1. Reaction of 8-Quinolinyl Ethyl Ketone and Olefins

entry

catalyst

1 2 3 4

(PPh3)3RhCl [Rh(COD)Cl]2 [Rh(Cp*)Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2 [Rh(COD) Cl2]2

5

under similar reaction conditions, 8-quinolinyl phenyl ketone produces styrene via ethylene insertion into a rhodium−phenyl bond and β-elimination of the resulting phenylethyl complex. The exchange reaction with alkenes other than ethylene was inefficient in such a reaction system because β-elimination of the produced alkylrhodium intermediate was relatively fast to compete with the reductive elimination process.18 However, our recent study indicates that β-elimination could be significantly inhibited by a bidentate phosphine ligand, which enables reductive elimination to be the major process for olefins other than ethylene (Scheme 1, path b). Herein, we report the alkyl group exchange reaction of 8-acetylquinoline with olefins through chelation-assisted rhodium-catalyzed C− C bond activation.

6 7 8 9 10 11 12 13

■

14

RESULTS AND DISCUSSION 1-(Quinolin-8-yl)propan-1-one (1a) and styrene (2a) were initially used as substrates for the optimization of reaction conditions (Table 1). By application of (Ph3P)3RhCl and [Rh(Cp*)Cl2]2 as catalysts to the reaction system, the desired product was obtained in the reaction mixture after 24 h at 160 °C, but with low yield. Most of 1a remained in the reaction mixture. Given that a molar excess of 2a was used, the presence of a starting material indicates that catalyst deactivation had occurred rather than equilibrium. The slow reductive elimination process that competed with fast β-elimination may inhibit the production of 3a in this case. This result is consistent with the previous report of Suggs and Jun.18 When [Rh(COD)Cl]2 was used as the catalyst, the reactions of 1a and 2a produced the desired product 3a under similar reaction conditions, but with low yield (8%). This finding indicates that the ligand may play an important role in the formation of product 3a. Then, different ligands were screened by using [Rh(COD)Cl]2 as a catalyst precursor. The addition of PCy3 slightly improved the yield of 3a (12%) after the reaction time was extended to 72 h. The phosphine ligands (mMeOC6H4)3P, P(C6F5)3, and (p-CF3C6H4)3P improved the yield of 3a to 57%, 24%, and 55%, respectively, under similar reaction conditions. Bidentate phosphine ligands, such as 1,2bis(diphenylphosphino)ethane and 1,1′-bis(diphenylphosphino)ferrocene, could also improve the product yields to 56% and 38%, respectively. However, the ligand rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene inhibits the reaction. Only a 6% yield of 3a was isolated. 1,3Bis(diphenylphosphino)propane (DPPP) exhibited better results in comparison other ligands. The yield of 3a was 63%, which was further improved to 71% when the reaction time was prolonged to 168 h. Different bases affected the reaction. For example, CyNH2 prevents the catalytic reaction

15 16

time (h)

yield (%)b

24 24 24 72

4 8 2 12

(mMeOC6H4)3P P(C6F5)3)

72

57

72

24

(p-CF3C6H4)3P

72

55

DPPE

72

56

DPPP

72

63

rac-BINP

72

6

DPPF

72

38

DPPP

168

71

ligand

base

PCy3

DPPP

CyNH2

36

0

DPPP

DMF

36

56

DPPP

NEt3

36

73

DPPP

pyridine

36

51

a Reaction conditions: 1a (0.1 mmol), 2a (0.5 mmol), catalyst (10 mol % based on Rh), ligand (10 mol %), and base (2.5 equiv) in 0.5 mL of xylene at 160 °C. bIsolated yield.

system of [Rh(COD)Cl]2/DPPP, and no 3a was detected in the reaction mixture after 36 h. When N,N-dimethylformamide or pyridine was used as additive, the desired product was isolated in 56% or 51% yield, respectively. However, Et3N showed a positive effect when it was combined with the [Rh(COD)Cl]2/DPPP catalytic system, and 3a was obtained after 36 h with 73% yield. Thus, [Rh(COD)Cl]2/DPPP as the catalyst in combination with Et3N (2.5 equiv) was selected as the optimal catalytic system for the current transformation. With the optimal catalytic system, the effects of various substituent groups on this alkyl exchange reaction were investigated, and the results are shown in Table 2. When 1a was reacted with styrenes with a methyl group at the para, meta, and ortho positions, the desired products 3b−d were obtained in 74%, 76%, and 80% yields, respectively. These results show that slightly increasing the steric hindrance of styrenes improves the product yield of the corresponding product by slowing down the reaction rate of β-elimination. Styrenes with 2,5-Me2 and 2,4,6-Me3 substituents produced the desired products 3e,f, in 64% and 58% yields, respectively, which is lower than those of methyl-substituted styrenes. Such steric hindrance might work to the disadvantage of coordination of styrenes to the metal center, thus slowing down the yield of the product. Styrene with t-Bu at the para position reacted with 1a to produce 3g with 63% yield. oB

DOI: 10.1021/acs.organomet.8b00309 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics Table 2. Direct Functionalization of 1a with Various Substituted Olefinsa

a Reaction conditions: 1 (0.1 mmol), 2 (0.5 mmol), [Rh(COD)Cl]2 (5.0 mol %), ligand (10 mol %), and base (2.5 equiv) in 0.5 mL of xylene at 160 °C for 36 h. Isolated yields are given.

MeO-, m-MeO-, and p-MeO-substituted styrenes could also react with 1a to produce the corresponding products 3h−j in 65%, 69%, and 62% yields, respectively. Furthermore, a 3,4MeO2-substituted styrene reacted with 1a produced the product 3k in 53% yield. A styrene with a p-EtO group also produced the product 3l in medium yield (53%). Styrenes with an electron-withdrawing group at the para position, such as −COOMe, −CF3, and −CN, produced 3m−o in 58%, 59%, and 47% yields, respectively. However, a styrene with a strongly electron withdrawing group at the para position, such as −NO2, did not produce any product. This finding can be attributed to the low electron density of the π bond, which resulted from the electron-withdrawing effect that prevented the coordination to the metal center. Halogen-substituted styrenes were also applied for the reaction with 1a. However, the p-Cl- and p-Br-substituted styrenes yielded no product in the reaction with 1a. Styrene with a p-F substituent produced a product, but in low yield (28%). Other aryl ethylenes, such as 2-naphthalene, also reacted with 1a smoothly to produce a moderate yield (61%). An olefin containing a long aliphatic chain, such as methyl undec-10-enoate and 3,3-dimethylbut-1ene, could also react with 8-quinolinyl ethyl ketone but gave the desired products in 38% and 19% yields, respectively, indicating that the β-hydrogen elimination is fast for an olefin having a long aliphatic chain. On the basis of the experiments and previous reports on group-assisted C−C bond activation, a plausible catalytic mechanism is proposed and shown in Figure 1. The mechanistic pathway for the formation of 3 involves the following steps. First, the precursor of [Rh(COD)Cl] 2 converts to the more catalytically active catalyst I through ligand exchange of DPPP. Then, quinoline nitrogen coordinates with the metal center so that the metal and C− C bond are brought into proximity. Subsequently, the oxidative addition of the C−C bond to the Rh(I) metal center takes place to form the Rh(III) complex II. The resulting alkyl complex II β-eliminates a hydrogen to give the acylrhodium

Figure 1. Plausible mechanism for direct conversion of ethyl ketone to alkyl ketone via chelation-assisted rhodium(I) catalyzed carbon− carbon bond cleavage.

hydride intermediate III and releases an ethylene at the same time. The acylrhodium hydride intermediate III is trapped by styrene and yields the 2-phenylenthyl complex IV. Finally, the reductive elimination of the 2-phenylenthyl group and the 8acetyl quinoline ring from intermediate IV yields the desired product 3a, and the catalytic intermediate I further coordinates with 1a to regenerate II for another cycle. It is worth noting that the chelation of the bisphosphine ligand DPPP is beneficial to the reductive elimination process, including the process of IV to I and the reverse process of I to II.18,19 In this proposed reaction mechanism, the slow process of I to II C

DOI: 10.1021/acs.organomet.8b00309 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics

chromatography to give the final product 1-(quinolin-8-yl)propan-1one. General Experimental Procedure for the Rh-Catalyzed Synthesis of Quinolines by 1-(quinolin-8-yl)propan-1-one and Olefins. In an oven-dried screwed vial were placed the substituted 1-(quinolin-8-yl)propan-1-one (0.1 mmol), substituted styrene (0.5 mmol), [Rh(COD)Cl]2 (2.47 mg, 0.005 mmol), DPPP (diphenylphosphinopropane) (4.14 mg, 0.01 mmol), Et3N (25.3 mg, 0.25 mmol), and xylene (0.5 mL). The mixture was vigorously stirred at 160 °C for 36 h in an air atmosphere until the reaction was completed. The organic solvent was removed in vacuo, and the residue was then purified by column chromatography on silica gel to give the desired product. 3-Phenyl-1-(quinolin-8-yl)propan-1-one (3a). Purified by column chromatography to provide a yellow liquid (yield: 73%). The compound 3a is known. 1H NMR (400 MHz, CDCl3): δ 8.96 (dd, J = 4.2, 1.9 Hz, 1H), 8.20 (dd, J = 8.4, 1.8 Hz, 1H), 7.93 (d, J = 8.2 Hz, 1H), 7.86 (d, J = 7.1 Hz, 1H), 7.57 (t, J = 7.8 Hz, 1H), 7.45 (dd, J = 8.5, 4.2 Hz, 1H), 7.27 (q, J = 5.3, 3.7 Hz, 4H), 7.19 (q, J = 5.7, 4.2 Hz, 1H), 3.69 (t, J = 7.9 Hz, 2H), 3.14 (s, 2H). 13C NMR (101 MHz, CDCl3): δ 205.59, 150.49, 145.50, 141.56, 139.69, 136.23, 131.02, 129.20, 128.45, 128.34, 128.20, 126.07, 125.86, 121.44, 46.41, 30.52. Anal. Calcd (found) for C18H15NO: C, 82.80 (82.73); H, 5.81 (5.79); N, 5.35 (5.36). 1-(Quinolin-8-yl)-3-(p-tolyl)propan-1-one (3b). Purified by column chromatography to provide a yellow liquid (yield: 74%). 1H NMR (400 MHz, CDCl3): δ 8.85 (dd, J = 4.2, 1.8 Hz, 1H), 8.07 (dd, J = 8.3, 1.8 Hz, 1H), 7.78 (ddd, J = 18.8, 7.7, 1.5 Hz, 2H), 7.46 (s, 1H), 7.33 (dd, J = 8.3, 4.2 Hz, 1H), 7.06 (d, J = 7.9 Hz, 2H), 6.99 (d, J = 7.9 Hz, 2H), 3.58 (dd, J = 8.7, 7.1 Hz, 2H), 3.00 (t, J = 7.9 Hz, 2H), 2.21 (s, 3H). 13C NMR (101 MHz, CDCl3): δ 205.67, 150.42, 145.44, 139.66, 138.39, 136.17, 135.24, 130.94, 129.12, 128.98, 128.26, 128.15, 126.00, 121.37, 46.52, 30.04, 20.94. IR (KBr): v 2955, 2923, 2855, 1638, 1569, 1512, 1496, 1447, 1357, 1283, 1154, 793, 632 cm−1. ESI-MS: [M + Na]+ calcd for C19H17NO: 275.1301, found 298.1202. Anal. Calcd (found) for C19H17NO: C, 82.93 (82.88); H, 6.25 (6.22); N, 5.08 (5.09). 1-(Quinolin-8-yl)-3-(m-tolyl)propan-1-one (3c). Purified by column chromatography to provide a yellow liquid (yield: 76%). 1H NMR (400 MHz, CDCl3): δ 8.96 (dd, J = 4.2, 1.9 Hz, 1H), 8.18 (dd, J = 8.3, 1.8 Hz, 1H), 7.92 (dd, J = 8.2, 1.5 Hz, 1H), 7.85 (s, 1H), 7.57 (t, J = 7.6 Hz, 1H), 7.44 (dd, J = 8.3, 4.2 Hz, 1H), 7.17 (t, J = 7.5 Hz, 1H), 7.11−7.02 (m, 2H), 7.00 (d, J = 7.5 Hz, 1H), 3.68 (dd, J = 8.7, 7.1 Hz, 2H), 3.09 (t, J = 7.9 Hz, 2H), 2.32 (s, 3H). 13C NMR (101 MHz, CDCl3): δ 205.66, 150.47, 145.49, 141.46, 139.73, 137.85, 136.20, 130.96, 129.27, 129.15, 128.22, 128.18, 126.58, 126.04, 125.40, 121.41, 77.32, 77.00, 76.68, 46.44, 30.42, 21.39. IR (KBr): ν 2960, 2952, 2864, 1682, 1584, 1505, 1468, 1321, 1252, 1128, 1025, 768, 692 cm−1; ESI-MS: [M + Na]+ calcd for C19H17NO 275.1301, found 298.1200. Anal. Calcd (found) for C19H17NO: C, 82.93 (82.88); H, 6.19 (6.22); N, 5.10 (5.09). 1-(Quinolin-8-yl)-3-(o-tolyl)propan-1-one (3d). Purified by column chromatography to provide a yellow solid (yield: 80%). Mp: 41− 43 °C. 1H NMR (400 MHz, CDCl3): δ 8.92 (dd, J = 4.2, 1.8 Hz, 1H), 8.15 (dd, J = 8.3, 1.8 Hz, 1H), 7.88 (td, J = 7.9, 7.4, 1.5 Hz, 2H), 7.54 (dd, J = 8.1, 7.2 Hz, 1H), 7.40 (dd, J = 8.3, 4.2 Hz, 1H), 7.27−7.18 (m, 1H), 7.16−7.06 (m, 3H), 3.69−3.59 (m, 2H), 3.18−3.08 (m, 2H), 2.35 (s, 3H). 13C NMR (101 MHz, CDCl3): δ 205.72, 150.39, 145.44, 139.62, 139.60, 136.15, 136.06, 130.97, 130.06, 129.10, 128.67, 128.11, 125.98, 125.96, 125.90, 121.36, 44.99, 27.91, 19.27. IR (KBr): ν 3096, 2982, 2917, 1702, 1543, 1501, 1489, 874, 813 712 cm−1. ESI-MS: [M + Na]+ calcd for C19H17NO 275.1301, found 298.1205. Anal. Calcd (found) for C19H17NO: C, 83.00 (82.88); H, 6.21 (6.22); N, 5.07 (5.09). 3-(2,5-Dimethylphenyl)-1-(quinolin-8-yl)propan-1-one (3e). Purified by column chromatography to provide a yellow liquid (yield: 64%). 1H NMR (400 MHz, CDCl3): δ 8.96 (dd, J = 4.1, 1.8 Hz, 1H), 8.20 (dd, J = 8.3, 1.8 Hz, 1H), 7.91 (ddd, J = 17.5, 7.7, 1.5 Hz, 2H), 7.59 (t, J = 7.7 Hz, 1H), 7.45 (dd, J = 8.3, 4.1 Hz, 1H), 7.08−6.98 (m, 2H), 6.92 (dd, J = 7.6, 1.8 Hz, 1H), 3.68−3.55 (m, 2H), 3.09 (dd, J =

coincides with the reaction requiring high temperature and a long time. Et3N may have an important solvent effect during the coordination of DPPP or olefin with the rhodium catalyst.

■

CONCLUSION In summary, we developed a novel method for the synthesis of quinolinone derivatives. The method involves the exchange of the ethyl group of 1-(quinolin-8-yl)propan-1-one with substituted styrenes via group-directed C−C bond cleavage. In the presence of [Rh(COD)Cl]2 (5.0 mol %) along with Et3N (2.5 equiv) and DPPP (10 mol %), a series of substituted styrenes were reacted with 1-(quinolin-8-yl)propan-1-one to produce various substituted 3-phenyl-1-(quinolin-8-yl)propan1-ones in medium to good yields. Various functionalities were tolerated under the standard reaction conditions. Ligands were observed to play an important role in the inhibition of βhydrogen elimination. A bidentate phosphine ligand, i.e., DPPP, was identified to be the best ligand for this transformation. A plausible catalytic mechanism was proposed to explain the production of quinolinone derivatives. Further work on the applications of this reaction for generating quinolinone derivatives with biological activities is currently underway in our laboratory.

■

EXPERIMENTAL SECTION

General Information. 1H NMR, 13C NMR, and 19F NMR were recorded on a Bruker AV 400 MHz spectrometer with CDCl3 as solvent and tetramethylsilane as the internal standard. The chemical shifts are reported in ppm relative to CDCl3 (δ 7.26) for 1H NMR and relative to the central CDCl3 resonance (δ 77.0) for 13C NMR. In addition, (trifluoromethyl)benzene was used as an external standard for 19F NMR. NMR data of known compounds are in agreement with literature values. Coupling constants (J) are quoted in Hz at 400 MHz for 1H. Multiplicities are reported as follows: singlet (s), doublet (d), doublet of doublets (dd), triplet (t), quartet (q), and multiplet (m). 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 indicated, reactions were monitored by analytical thin-layer chromatography on a 0.20 mm silica gel plate and spots were detected by UV absorption. Flash chromatography was performed using silica gel (200−300 mesh) (from Yantai Huagong Chemical Co., Ltd.). The starting materials for the various styrenes were synthesized and purified according to literature procedures. Other chemicals or reagents were obtained from commercial sources. Experimental Details. For the preparation of 1-(quinolin-8yl)propan-1-one (1a), first quinoline-8-carbaldehyde (10 mmol) and anhydrous THF (8 mL) were placed in a dry three-necked flask under a nitrogen atmosphere, and the mixture was stirred at 30 °C until it completely dissolved. The prepared ethylmagnesium bromide was gradually added to the above mixture through a dry syringe, and the reaction mixture was continuously stirred at 30 °C for 4 h. It was then quenched with saturated aqueous NH4Cl and extracted several times with DCM. The organic phases were combined and dried with anhydrous MgSO4. The solvent was removed, and the residue was purified by column chromatography on silica gel with PE/EA 5/1 as eluent to give 1- (quinolin-8-yl)propan-1-ol. In the second step, pure 1-(quinolin-8-yl)propan-1-ol (10 mmol) was placed in a clean 50 mL flask, DCM (10 mL) was added, the mixture was stirred at room temperature, and Dess−Martin periodinane (20 mmol) was added. The reaction mixture was stirred for 40 min and then treated with saturated aqueous NaHCO3 and saturated aqueous sodium thiosulfate. The impurities were filtered off, and the filtrate was extracted several times with DCM. Organic phases were combined and dried with anhydrous MgSO4. After removal of the solvent, the residue was purified by silica gel column D

DOI: 10.1021/acs.organomet.8b00309 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics 9.1, 7.0 Hz, 2H), 2.30 (d, J = 12.6 Hz, 6H). 13C NMR (101 MHz, CDCl3): δ 205.87, 150.45, 145.53, 139.80, 139.45, 136.19, 135.29, 132.92, 130.96, 130.02, 129.59, 129.12, 128.18, 126.66, 126.05, 121.41, 45.15, 27.98, 20.94, 18.83. IR (KBr): ν 2956, 2923, 2853, 1640, 1496, 1461, 1378, 794, 647 cm−1. ESI-MS: [M + Na]+ calcd for C20H19NO 289.1467, found 312.1356. Anal. Calcd (found) for C20H19NO: C, 83.07 (83.01); H, 6.60 (6.62); N, 4.86 (4.84). 3-Mesityl-1-(quinolin-8-yl)propan-1-one (3f). Purified by column chromatography to provide a yellow solid (yield: 58%). Mp: 71−73 °C. 1H NMR (400 MHz, CDCl3): δ 8.93−8.87 (m, 1H), 8.15 (dd, J = 8.3, 1.9 Hz, 1H), 7.94−7.87 (m, 2H), 7.60−7.52 (m, 1H), 7.40 (dd, J = 8.3, 4.1 Hz, 1H), 6.83 (s, 2H), 3.51−3.41 (m, 2H), 3.18−3.06 (m, 2H), 2.34 (s, 6H),2.23 (s, 3H). 13C NMR (101 MHz, CDCl3): δ 205.47, 150.32, 143.96, 138.10, 136.24, 135.28, 134.90, 134.87, 131.72, 130.52, 128.88, 128.37, 126.64, 121.76, 77.31, 77.00, 76.68, 43.12, 24.20, 20.78, 19.75. IR (KBr): ν 2954, 2922, 2855, 1681, 1569, 1493, 1459, 1378, 1354, 1285, 1258, 1169, 1101, 969, 831, 793, 763 cm−1. ESI-MS: [M + Na]+ calcd for C21H21NO 303.1623, found 326.1514. Anal. Calcd (found) for C21H21NO: C, 83.11 (83.13); H, 6.96 (6.98); N, 4.63 (4.62). 3-(4-(tert-Butyl)phenyl)-1-(quinolin-8-yl)propan-1-one (3g). Purified by column chromatography to provide a yellow liquid (yield: 63%). 1H NMR (400 MHz, CDCl3): δ 8.89−8.75 (m, 1H), 8.05 (d, J = 8.2 Hz, 1H), 7.77 (dd, J = 13.9, 7.7 Hz, 2H), 7.44 (t, J = 7.9 Hz, 1H), 7.35−7.26 (m, 1H), 7.25−6.96 (m, 4H), 3.59 (t, J = 7.9 Hz, 2H), 3.01 (t, J = 8.0 Hz, 2H), 1.20 (s, 9H). 13C NMR (101 MHz, CDCl3): δ 205.71, 150.41, 148.58, 145.43, 139.69, 138.39, 136.16, 130.93, 129.11, 128.12, 128.04, 125.98, 125.18, 121.35, 46.34, 34.27, 31.34, 29.94. IR (KBr): ν 2972, 2928, 2856, 1684, 1606, 1513, 1501, 1496, 1489, 1276, 1153, 985, 821, 796, 653 cm−1. ESI-MS: [M + Na]+ calcd for C22H23NO 317.1780, found 340.1676; Anal. Calcd (found) for C23H23NO: C, 83.21 (83.24); H, 7.33 (7.30); N, 4.40 (4.41). 3-(2-Methoxyphenyl)-1-(quinolin-8-yl)propan-1-one (3h). Purified by column chromatography to provide a yellow liquid (yield: 62%). 1H NMR (400 MHz, CDCl3): δ 8.85 (dd, J = 4.3, 1.7 Hz, 1H), 8.08 (dd, J = 8.4, 1.8 Hz, 1H), 7.83−7.72 (m, 2H), 7.47 (t, J = 7.6 Hz, 1H), 7.33 (dd, J = 8.4, 4.2 Hz, 1H), 7.18−7.04 (m, 2H), 6.83−6.69 (m, 2H), 3.69 (s, 3H), 3.60−3.53 (m, 2H), 3.03 (t, J = 7.8 Hz, 2H). 13 C NMR (101 MHz, CDCl3): δ 206.16, 157.49, 150.40, 145.44, 139.94, 136.12, 130.74, 129.92, 129.75, 128.96, 128.13, 127.13, 125.97, 121.33, 120.29, 110.06, 55.11, 44.66, 25.38. IR (KBr): ν 6976, 2924, 2854, 1675, 1566, 1490, 1459, 1239, 1168, 1104, 1026, 829, 792, 749 cm−1. ESI-MS: [M + H]+ calcd for C19H17NO2 291.1259, found 292.1336. Anal. Calcd (found) for C19H17NO2: C, 78.36 (78.33); H, 5.86 (5.88); N, 4.80 (4.81). 3-(3-Methoxyphenyl)-1-(quinolin-8-yl)propan-1-one (3i). Purified by column chromatography to provide a yellow liquid (yield: 69%). 1H NMR (400 MHz, CDCl3): δ 8.88−8.80 (m, 1H), 8.07 (dd, J = 8.3, 1.8 Hz, 1H), 7.79 (ddd, J = 16.7, 7.7, 1.5 Hz, 2H), 7.46 (dd, J = 8.1, 7.1 Hz, 1H), 7.33 (dd, J = 8.3, 4.2 Hz, 1H), 7.10 (t, J = 7.8 Hz, 1H), 6.82−6.70 (m, 2H), 6.65 (td, J = 8.3, 2.4 Hz, 1H), 3.68 (s, 3H), 3.64−3.56 (m, 2H), 3.06−2.99 (m, 2H). 13C NMR (101 MHz, CDCl3): δ 205.48, 159.59, 150.46, 145.49, 143.19, 139.65, 136.21, 131.01, 129.27, 129.20, 128.19, 126.04, 121.41, 120.82, 114.14, 111.24, 55.09, 46.27, 30.55. IR (KBr): ν 2986, 2971, 2885, 1690, 1596, 1512, 1465, 1341, 1206, 1125, 1052, 781, 715 cm−1. ESI-MS: [M + Na]+ calcd for C19H17NO2 291.1259, found 314.1156. Anal. Calcd (found) for C19H17NO2: C, 78.35 (78.33); H, 5.89 (5.89); N, 4.83 (4.81). 3-(4-Methoxyphenyl)-1-(quinolin-8-yl)propan-1-one (3j). Purified by column chromatography to provide a yellow liquid (yield: 62%). 1H NMR (400 MHz, CDCl3): δ 8.83 (d, J = 2.3 Hz, 1H), 8.05 (d, J = 8.4 Hz, 1H), 7.76 (dd, J = 20.0, 7.7 Hz, 2H), 7.44 (t, J = 7.9 Hz, 1H), 7.35−7.25 (m, 1H), 7.07 (d, J = 8.0 Hz, 2H), 6.71 (d, J = 8.0 Hz, 2H), 3.66 (s, 3H), 3.56 (dd, J = 15.1, 7.2 Hz, 2H), 2.97 (t, J = 7.9 Hz, 2H). 13C NMR (101 MHz, CDCl3):δ205.71, 157.80, 150.46, 145.52, 139.78, 136.21, 133.61, 130.96, 129.34, 129.17, 128.20, 126.06, 121.41, 113.76, 55.23, 46.67, 29.65. IR (KBr): ν 2965, 2923, 2852, 1679, 1658, 1641, 1500, 1251, 1114, 1053, 812, 768, 651 cm−1. ESI-MS: [M + Na]+ calcd for C19H17NO2 291.1259, found 314.1159.

Anal. Calcd (found) for C19H17NO2: C, 78.32 (78.33); H, 5.89 (5.88); N, 4.82 (4.81). 3-(3,4-Dimethoxyphenyl)-1-(quinolin-8-yl)propan-1-one (3k). Purified by column chromatography to provide a yellow solid (yield: 53%). Mp: 92−94 °C. 1H NMR (400 MHz, CDCl3): δ 8.95 (dd, J = 4.2, 1.8 Hz, 1H), 8.19 (dd, J = 8.3, 1.8 Hz, 1H), 7.92 (dd, J = 8.2, 1.5 Hz, 1H), 7.84 (dd, J = 7.1, 1.5 Hz, 1H), 7.56 (dd, J = 8.2, 7.2 Hz, 1H), 7.44 (dd, J = 8.3, 4.2 Hz, 1H), 6.85−6.74 (m, 3H), 3.85 (d, J = 3.9 Hz, 6H), 3.67 (dd, J = 8.3, 7.1 Hz, 2H), 3.08 (t, J = 7.7 Hz, 2H). 13 C NMR (101 MHz, CDCl3): δ 205.66, 150.44, 148.70, 147.14, 145.45, 139.71, 136.23, 134.15, 130.99, 129.14, 128.18, 126.04, 121.42, 120.17, 111.80, 111.15, 55.86, 55.74, 46.57, 30.09. IR (KBr): ν 2965, 2925, 2850, 1675, 1565, 1510, 1459, 1257, 1138, 1024, 793, 760 cm−1. ESI-MS: [M + Na]+ calcd for C20H19NO3 321.1365, found 344.1255. Anal. Calcd (found) for C20H19NO3: C, 74.74 (74.75); H, 5.97 (5.96); N, 4.36 (4.36). 3-(4-Ethoxyphenyl)-1-(quinolin-8-yl)propan-1-one (3l). Purified by column chromatography to provide a yellow liquid (yield: 53%). 1 H NMR (400 MHz, CDCl3): δ 8.94 (dd, J = 4.2, 1.8 Hz, 1H), 8.16 (dd, J = 8.3, 1.8 Hz, 1H), 7.90 (dd, J = 8.2, 1.5 Hz, 1H), 7.83 (dd, J = 7.1, 1.5 Hz, 1H), 7.55 (dd, J = 8.2, 7.2 Hz, 1H), 7.42 (dd, J = 8.3, 4.2 Hz, 1H), 7.19−7.10 (m, 2H), 6.84−6.76 (m, 2H), 3.99 (q, J = 7.0 Hz, 2H), 3.65 (dd, J = 8.6, 7.1 Hz, 2H), 3.12−2.99 (m, 2H), 1.38 (t, J = 7.0 Hz, 3H). 13C NMR (101 MHz, CDCl3): δ 205.74, 157.09, 150.42, 145.43, 139.72, 136.17, 133.40, 130.91, 129.27, 129.08, 128.14, 126.00, 121.37, 114.31, 63.32, 46.64, 29.61, 14.83. IR (KBr): ν 2955, 2922, 2852, 1641, 1568, 1507, 1387, 1237, 1172, 1110, 1044, 969, 918, 789, 647 cm−1. ESI-MS: [M + Na]+ calcd for C20H19NO2 305.1416, found 328.1303. Anal. Calcd (found) for C20H19NO2: C, 78.69 (78.66); H, 6.28 (6.27); N, 4.57 (4.59). Methyl 4-(3-Oxo-3-(quinolin-8-yl)propyl)benzoate (3m). Purified by column chromatography to provide a yellow liquid (yield: 58%). 1 H NMR (400 MHz, CDCl3): δ 8.98−8.90 (m, 1H), 8.18 (dd, J = 8.3, 1.8 Hz, 1H), 8.01−7.89 (m, 3H), 7.89−7.81 (m, 1H), 7.62−7.51 (m, 1H), 7.44 (dd, J = 8.3, 4.1 Hz, 1H), 7.34 (d, J = 8.0 Hz, 2H), 3.89 (s, 3H), 3.72 (t, J = 7.7 Hz, 2H), 3.19 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ 204.89, 167.04, 150.44, 147.13, 145.45, 139.33, 136.24, 131.17, 129.64, 129.30, 128.48, 128.17, 127.81, 126.03, 121.43, 51.91, 45.76, 30.44. IR (KBr): ν 2954, 2924, 2853, 1716, 1674, 1610, 1567, 1494, 1433, 1277, 1178, 1105, 1018, 967, 829, 792, 760,702 cm−1. ESI-MS: [M + Na]+ calcd for C20H17NO3 319.1208, found 342.1110. Anal. Calcd (found) for C20H17NO3: C, 75.25 (75.21); H, 5.36 (5.37); N, 4.41 (4.39). 1-(Quinolin-8-yl)-3-(4-(trifluoromethyl)phenyl)propan-1-one (3n). Purified by column chromatography to provide a yellow solid (yield: 59%). Mp: 42−45 °C. 1H NMR (400 MHz, CDCl3): δ 8.86 (dd, J = 4.2, 1.9 Hz, 1H), 8.11 (dd, J = 8.3, 1.8 Hz, 1H), 7.82 (ddd, J = 19.8, 7.7, 1.5 Hz, 2H), 7.54−7.41 (m, 3H), 7.36 (dd, J = 8.3, 4.2 Hz, 1H), 7.30 (d, J = 8.0 Hz, 2H), 3.68−3.61 (m, 2H), 3.11 (t, J = 7.6 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ 204.81, 150.47, 145.75, 145.51, 139.27, 136.31, 131.28, 129.41, 128.79, 128.23, 127.00 (d, J = 270 Hz), 126.07, 125,21 (d, J = 4 Hz), 121.47, 45.81, 30.26. 19F NMR (376 MHz, CDCl3): δ −62.29 (s, 3F). IR (KBr): ν 2956, 2924, 2851, 1639, 1494, 1459, 1378, 1325, 1163, 1120, 1087, 972, 827, 792 cm−1. ESI-MS: [M + Na]+ calcd for C19H14F3NO 329.1027, found 352.0920. Anal. Calcd (found) for C19H14F3NO: C, 69.33 (69.30); H, 4.29 (4.29); N, 4.24 (4.25). 4-(3-Oxo-3-(quinolin-8-yl)propyl)benzonitrile (3o). Purified by column chromatography to provide a yellow solid (yield: 47%). Mp: 91−94 °C. 1H NMR (400 MHz, CDCl3): δ 8.95 (dd, J = 4.2, 1.8 Hz, 1H), 8.21 (dd, J = 8.3, 1.8 Hz, 1H), 7.95 (dd, J = 8.2, 1.4 Hz, 1H), 7.89 (dd, J = 7.2, 1.4 Hz, 1H), 7.58 (dd, J = 10.7, 7.9 Hz, 3H), 7.46 (dd, J = 8.3, 4.2 Hz, 1H), 7.39 (d, J = 8.0 Hz, 2H), 3.75 (t, J = 7.5 Hz, 2H), 3.21 (t, J = 7.5 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ 204.41, 150.45, 147.34, 139.01, 136.33, 132.10, 131.40, 129.47, 129.31, 128.20, 126.06, 121.48, 119.08, 109.64, 45.41, 30.49. . IR (KBr): ν 2957, 2925, 2855, 2315, 1638, 1510, 1482, 1415, 1336, 1174, 1135, 986, 832, 647 cm−1. ESI-MS: [M + Na]+ calcd for C19H14N2O 286.1106, found 309.0996. Anal. Calcd (found) for C19H14N2O: C, 79.67 (79.70); H, 4.94 (4.93); N, 9.77 (9.78). E

DOI: 10.1021/acs.organomet.8b00309 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics 3-(4-Fluorophenyl)-1-(quinolin-8-yl)propan-1-one (3p). Purified by column chromatography to provide a yellow liquid (yield: 28%). 1 H NMR (400 MHz, CDCl3): δ 8.96 (dd, J = 4.1, 1.8 Hz, 1H), 8.19 (dd, J = 8.3, 1.8 Hz, 1H), 7.92 (dd, J = 8.1, 1.5 Hz, 1H), 7.85 (dd, J = 7.2, 1.5 Hz, 1H), 7.57 (t, J = 7.6 Hz, 1H), 7.45 (dd, J = 8.3, 4.2 Hz, 1H), 7.22 (dd, J = 8.4, 5.4 Hz, 2H), 6.95 (t, J = 8.7 Hz, 2H), 3.67 (t, J = 7.7 Hz, 2H), 3.10 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ 205.33, 161.23 (d, J = 242 Hz), 150.47, 145.47, 139.54, 137.12, 136.26, 131.11, 129.84, 129.76, 129.24, 128.20, 126.06, 121.45, 115.12, 114.91, 46.41, 29.66. 19F NMR (376 MHz, CDCl3): δ −117.69 (s, 1F). IR (KBr): ν 2956, 2924, 2854, 1681, 1601, 1568, 1508, 1460, 1376, 1222, 1159, 828, 793 cm−1. ESI-MS: [M + Na]+ calcd for C18H14FNO 279.1059, found 302.0947. Anal. Calcd (found) for C18H14FNO: C, 77.41 (77.40); H, 5.04 (5.05); N, 5.00 (5.01). 3-(Naphthalen-2-yl)-1-(quinolin-8-yl)propan-1-one (3t). Purified by column chromatography to provide a yellow liquid (yield: 61%). 1 H NMR (400 MHz, CDCl3): δ 8.95 (d, J = 3.8 Hz, 1H), 8.15 (d, J = 8.3 Hz, 1H), 7.87 (dd, J = 11.9, 8.2 Hz, 2H), 7.81−7.65 (m, 4H), 7.54 (t, J = 8.2 Hz, 1H), 7.40 (d, J = 7.5 Hz, 4H), 3.78 (t, J = 7.9 Hz, 2H), 3.29 (t, J = 8.0 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ 205.45, 150.46, 145.51, 139.65, 139.07, 136.20, 133.58, 131.98, 131.02, 129.22, 128.19, 127.84, 127.53, 127.41, 127.33, 126.44, 126.04, 125.82, 125.11, 121.41, 46.29, 30.65. IR (KBr): ν 2951, 2922, 2852, 1638, 1569, 1495, 1461, 1256, 792, 745, 650 cm−1. ESI-MS: [M + Na]+ calcd for C22H17NO 311.1310, found 334.1195. Anal. Calcd (found) for C22H17NO: C, 84.87 (84.86); H, 5.50 (5.50); N, 4.51 (4.50). Methyl 12-Oxo-12-(quinolin-8-yl)dodecanoate (3u). Purified by column chromatography to provide a yellow liquid (yield: 38%). 1H NMR (400 MHz, CDCl3): δ 8.96 (d, J = 4.2 Hz, 1H), 8.19 (d, J = 8.2 Hz, 1H), 7.91 (d, J = 8.2 Hz, 1H), 7.83 (d, J = 7.1 Hz, 1H), 7.58 (t, J = 7.6 Hz, 1H), 7.45 (dd, J = 8.4, 4.2 Hz, 1H), 3.66 (s, 3H), 3.31 (t, J = 7.6 Hz, 2H), 2.30 (t, J = 7.6 Hz, 2H), 1.75 (p, J = 7.5 Hz, 2H), 1.64−1.58 (m, 2H), 1.29 (d, J = 12.4 Hz, 12H). 13C NMR (101 MHz, CDCl3): δ 207.13, 174.33, 150.45, 145.48, 140.34, 136.19, 130.62, 128.70, 128.22, 126.06, 121.41, 51.44, 44.92, 34.12, 29.42, 29.40, 29.32, 29.24, 29.14, 24.96, 24.41. IR (KBr): ν 2971, 2926, 2852, 1736, 1641, 1550, 1494, 1459, 1364, 1257, 1201, 794, 761 cm−1. ESI-MS: [M + Na]+ calcd for C22H29NO3 355.2147, found 378.2047. Anal. Calcd (found) for C22H29NO3: C, 74.37 (74.33); H, 8.20 (8.22); N, 3.93 (3.94). 4,4-Dimethyl-1-(quinolin-8-yl)pentan-1-one (3v). Purified by column chromatography to provide a yellow liquid (yield: 19%). 1H NMR (400 MHz, CDCl3): δ 8.96 (dd, J = 4.2, 1.8 Hz, 1H), 8.19 (dd, J = 8.3, 1.8 Hz, 1H), 7.91 (dd, J = 8.2, 1.5 Hz, 1H), 7.84 (dd, J = 7.2, 1.5 Hz, 1H), 7.57 (t, J = 7.6 Hz, 1H), 7.44 (dd, J = 8.3, 4.2 Hz, 1H), 3.33−3.26 (m, 2H), 1.72−1.65 (m, 2H), 0.92 (s, 9H). 13C NMR (101 MHz, CDCl3): δ 207.64, 150.41, 145.43, 140.31, 136.16, 130.63, 128.80, 128.19, 126.03, 121.39, 40.70, 38.00, 30.19, 29.23. IR (KBr): ν 2955, 2925, 2855, 1643, 1494, 1461, 1377, 1259, 1099, 1025, 795, 647 cm−1. ESI-MS: [M + Na]+ calcd for C16H19NO 241.1467, found 264.1359. Anal. Calcd (found) for C16H19NO: C, 79.59 (79.63); H, 7.92 (7.94); N, 5.79 (5.80).

■

ORCID

Tao Wang: 0000-0003-2675-7039 Jianhui Wang: 0000-0003-2581-7247 Notes

The authors declare no competing financial interest.

■

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 (16JCYBJC19700).

■

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.8b00309. NMR spectra for compounds and complexes synthesized

■

REFERENCES

(1) (a) Xu, T.; Dermenci, A.; Dong, G. Transition Metal-Catalyzed C−C Bond Activation of Four-Membered Cyclic Ketones. Top. Curr. Chem. 2014, 346, 233−257. (b) Jun, C.-H.; Park, J. W. Directed C − C Bond Activation by Transition Metal Complexes. Top. Organomet. Chem. 2007, 24, 117−143. (c) Rong, Z.-Q.; Lim, H. N.; Dong, G. Intramolecular Acetyl Transfer to Olefins by Catalytic C-C Bond Activation of Unstrained Ketones. Angew. Chem., Int. Ed. 2018, 57, 475−479. (d) Xia, Y.; Wang, J.; Dong, G. Suzuki-Miyaura Coupling of Simple Ketones via Activation of Unstrained Carbon-Carbon Bonds. J. Am. Chem. Soc. 2018, 140, 5347−5351. (e) Murakami, M.; Ito, Y. Cleavage of Carbon-Carbon Single Bonds by Transition Metals. Top. Organomet. Chem. 1999, 3, 97−129. (f) Onodera, S.; Ishikawa, S.; Kochi, T.; Kakiuchi, F. Direct Alkenylation of Allylbenzenes via Chelation-Assisted C−C Bond Cleavage. J. Am. Chem. Soc. 2018, DOI: 10.1021/jacs.8b03718. (2) For reviews of C−C bond activation see: (a) Souillart, L.; Cramer, N. Catalytic C-C Bond Activations via Oxidative Addition to Transition Metals. Chem. Rev. 2015, 115, 9410−9464. (b) Chen, F.; Wang, T.; Jiao, N. Recent advances in transition-metal-catalyzed functionalization of unstrained carbon-carbon bonds. Chem. Rev. 2014, 114, 8613−8661. (c) Dermenci, A.; Coe, J. W.; Dong, G. Direct Activation of Relatively Unstrained Carbon-Carbon Bonds in Homogeneous Systems. Org. Chem. Front. 2014, 1, 567−581. (d) Mack, D. J.; Njardarson, J. T. Recent Advances in the MetalCatalyzed Ring Expansions of Three- and Four-Membered Rings. ACS Catal. 2013, 3, 272−286. (e) Ruhland, K. Transition-MetalMediated Cleavage and Activation of C−C Single Bonds. Eur. J. Org. Chem. 2012, 2012, 2683−2706. (f) Jun, C.-H. Transition metalcatalyzed carbon-carbon bond activation. Chem. Soc. Rev. 2004, 33, 610−618. (g) Murakami, M.; Matsuda, T. Metal-catalysed cleavage of carbon-carbon bonds. Chem. Commun. 2011, 47, 1100−1105. (h) Hoang, G. T.; Walsh, D. J.; McGarry, K. A.; Anderson, C. B.; Douglas, C. J. Anderson and Christopher J. Douglas. Development and Mechanistic Study of Quinoline-Directed Acyl C-O Bond Activation and Alkene Oxyacylation Reactions. J. Org. Chem. 2017, 82, 2972−2983. (i) Jun, C.-H.; Han, J.-S.; Kang, J.-B.; Kim, S.-I. Catalytic and Stoichiometric Hydroacylation of Olefin Derivatives with 8-Quinolinecarboxaldehyde by Rh(I). Bull. Korean Chem. Soc. 1994, 15, 204−209. (j) Kim, D.-S.; Park, W.-J.; Jun, C.-H. Metal− Organic Cooperative Catalysis in C−H and C-C Bond Activation. Chem. Rev. 2017, 117, 8977−9015. (k) Seiser, T.; Saget, T.; Tran, D. N.; Cramer, N. Cyclobutanes in catalysis. Angew. Chem., Int. Ed. 2011, 50, 7740−7752. (l) Rybtchinski, B.; Milstein, D. Metal Insertion into C−C Bonds in Solution. Angew. Chem., Int. Ed. 1999, 38, 870−883. (m) Jones, W. D. The fall of the C-C bond. Nature 1993, 364, 676− 677. (3) For selected recent C−C bond activation reactions, see: (a) Guo, W.; Wu, S.; Wang, T.; Xie, Q.; Duan, Y.; Luo, S.; Wang, J.; Yu, X. Rhodium-catalyzed decarbonylative cycloadditions of 1Hindene-1,2,3-triones and alkynes via direct C−C bond activation: divergent synthesis of indenones and quinones. Org. Chem. Front. 2018, 5, 1613−1621. (b) Yu, X.; Wang, J.; Guo, W.; Tian, Y.; Wang, J. Efficient Approach To Construct Unsymmetrical Biaryls through Oxidative Coupling Reactions of Aromatic Primary Alcohols and

(PDF)

AUTHOR INFORMATION

Corresponding Authors

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

DOI: 10.1021/acs.organomet.8b00309 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics Arylboronic Acids with a Rhodium Catalyst. Organometallics 2016, 35, 1876−1884. (c) Dennis, J. M.; Compagner, C. T.; Dorn, S. K.; Johnson, J. B. Rhodium-Catalyzed Interconversion of Quinolinyl Ketones with Boronic Acids via C-C Bond Activation. Org. Lett. 2016, 18, 3334−3337. (d) Chen, K.; Liu, J.-X.; Tang, X.-Y.; Shi, M. Rh(I) Catalysts and Substrates Controlled Selective C-C Bonds Activation of Benzyl Sulfonamide/Alcohol-tethered Alkylidenecyclopropanes. Chem. - Eur. J. 2016, 22, 11549−11553. (e) Feng, S.; Mo, F.-Y.; Xia, Y.; Liu, Z.-X.; Liu, Z.; Zhang, Y.; Wang, J.-B. Rhodium(I)Catalyzed C−C Bond Activation of Siloxyvinylcyclopropanes with Diazoesters. Angew. Chem. 2016, 128, 15627−15631. (f) Wang, G. W.; McCreanor, N. G.; Shaw, M. H.; Whittingham, W. G.; Bower, J. F. New Initiation Modes for Directed Carbonylative C−C Bond Activation: Rhodium-Catalyzed (3 + 1 + 2) Cycloadditions of Aminomethylcyclopropanes. J. Am. Chem. Soc. 2016, 138, 13501− 13504. (g) Wu, J. Q.; Qiu, Z. P.; Zhang, S. S.; Liu, J. G.; Lao, Y. X.; Gu, L. Q.; Huang, Z. S.; Li, J.; Wang, H. G. Rhodium(III)-catalyzed C-H/C-C activation sequence: vinylcyclopropanes as versatile synthons in direct C-H allylation reactions. Chem. Commun. 2015, 51, 77−80. (h) Shaw, M. H.; McCreanor, N. G.; Whittingham, W. G.; Bower, J. F. Reversible C-C bond activation enables stereocontrol in Rh-catalyzed carbonylative cycloadditions of aminocyclopropanes. J. Am. Chem. Soc. 2015, 137, 463−468. (i) Feng, P.; Sun, X.; Su, Y. J.; Li, X. Y.; Zhang, L.-H.; Shi, X.-D.; Jiao, N. Ceric ammonium nitrate (CAN) catalyzed modification of ketones via two C-C bond cleavages with the retention of the oxo-group. Org. Lett. 2014, 16, 3388−3391. (j) Gu, L.-J.; Jin, C.; Zhang, H.-T.; Zhang, L.-Z. Copper-catalyzed aerobic oxidative cleavage of C-C bonds in epoxides leading to aryl ketones. J. Org. Chem. 2014, 79, 8453−8456. (k) Zhang, J.; Wu, D.G.; Chen, X.-L.; Liu, Y.-K.; Xu, Z.-Y. Copper-Catalyzed Oxidative Cyclization of 1,5-Enynes with Concomitant C-C Bond Cleavage: An Unexpected Access to 3-Formyl-1-indenone Derivatives. J. Org. Chem. 2014, 79, 4799−4808. (l) Wang, Y.; Kang, Q. Palladium-catalyzed allylic esterification via C-C bond cleavage of a secondary homoallyl alcohol. Org. Lett. 2014, 16, 4190−4193. (m) Aïssa, C.; Crépin, D.; Tetlow, D. J.; Ho, K. Y. T. Multiple Rhodium-Catalyzed Cleavages of Single C−C bonds. Org. Lett. 2013, 15, 1322−1325. (n) Ishida, N.; Ikemoto, W.; Murakami, M. Cleavage of C-C and C-Si σ-Bonds and Their Intramolecular Exchange. J. Am. Chem. Soc. 2014, 136, 5912− 5915. (o) Xia, Y.; Liu, Z. X.; Liu, Z.; Ge, R.; Ye, F.; Hossain, M.; Zhang, Y.; Wang, J.-B. Formal Carbene Insertion into C-C Bond: Rh(I)-Catalyzed Reaction of Benzocyclobutenols with Diazoesters. J. Am. Chem. Soc. 2014, 136, 3013−3015. (p) Souillart, L.; Parker, E.; Cramer, N. Highly enantioselective rhodium(I)-catalyzed activation of enantiotopic cyclobutanone c-c bonds. Angew. Chem., Int. Ed. 2014, 53, 3001−3005. (q) Yu, H.-Z.; Wang, C.; Yang, Y.-M.; Dang, Z.-M. Mechanistic Study on Rh-Catalyzed Stereoselective C-C/C-H Activation of tert-Cyclobutanols. Chem. - Eur. J. 2014, 20, 3839− 3848. (r) Xu, T.; Dong, G. Coupling Sterically Hindered Trisubstituted Olefin and Benzocyclobutenones via C-C Activation: Total Synthesis and Structural Revision of Cycloinumakiol. Angew. Chem., Int. Ed. 2014, 53, 10733−10736. (s) Parker, E.; Cramer, N. Asymmetric Rhodium(I)-Catalyzed C-C Activations with Zwitterionic Bis-phospholane Ligands. Organometallics 2014, 33, 780−787. (t) Souillart, L.; Cramer, N. Highly enantioselective rhodium(I)catalyzed carbonyl carboacylations initiated by C-C bond activation. Angew. Chem., Int. Ed. 2014, 53, 9640−9644. (u) Zhang, C.; Feng, P.; Jiao, N. Cu-Catalyzed Esterification Reaction via Aerobic Oxygenation and C-C Bond Cleavage: An Approach toα-Ketoesters. J. Am. Chem. Soc. 2013, 135, 15257−15262. (v) Xu, T.; Dong, G. RhCatalyzed Lewis Acid-Promoted Regioselective Carboacylation of Olefins: A C−C Activation Approach to Access Fused-Ring Systems. Angew. Chem., Int. Ed. 2012, 51, 7567−7571. (w) Youn, S. W.; Kim, B. S.; Jagdale, A. R. Pd-catalyzed sequential C-C bond formation and cleavage: evidence for an unexpected generation of arylpalladium(II) species. J. Am. Chem. Soc. 2012, 134, 11308−11311. (x) Wang, J.; Liu, B.; Zhao, H.; Wang, J. Rhodium-Catalyzed Cross-Coupling Reactions of Carboxylate and Organoboron Compounds via Chelation-Assisted C−C Bond Activation. Organometallics 2012, 31, 8598−8607.

(4) Chatani, N.; Ie, Y.; Kakiuchi, F.; Murai, S. Ru3(CO)12-Catalyzed Decarbonylative Cleavage of a C−C Bond of Alkyl Phenyl Ketones. J. Am. Chem. Soc. 1999, 121, 8645−8646. (5) Jun, C.-H.; Lee, H. Catalytic Carbon−Carbon Bond Activation of Unstrained Ketone by Soluble Transition-Metal Complex. J. Am. Chem. Soc. 1999, 121, 880−881. (6) Wentzel, M. T.; Reddy, V. J.; Hyster, T. K.; Douglas, C. J. Chemoselectivity in catalytic C-C and C-H bond activation: controlling intermolecular carboacylation and hydroarylation of alkenes. Angew. Chem., Int. Ed. 2009, 48, 6121−6123. (7) Dreis, A. M.; Douglas, C. J. Catalytic carbon-carbon sigma bond activation: an intramolecular carbo-acylation reaction with acylquinolines. J. Am. Chem. Soc. 2009, 131, 412−413. (8) (a) Rathbun, C. M.; Johnson, J. B. Rhodium-catalyzed acylation with quinolinyl ketones: carbon-carbon single bond activation as the turnover-limiting step of catalysis. J. Am. Chem. Soc. 2011, 133, 2031− 2033. (b) Lutz, J. P.; Rathbun, C. M.; Stevenson, S. M.; Powell, B. M.; Boman, T. S.; Baxter, C. E.; Zona, J. M.; John-son, J. B. Rate-limiting step of the Rh-catalyzed carboacylation of alkenes: C-C bond activation or migratory insertion? J. Am. Chem. Soc. 2012, 134, 715−722. (9) Xu, T.; Ko, H. M.; Savage, N. A.; Dong, G. Highly enantioselective Rh-catalyzed carboacylation of olefins: efficient syntheses of chiral poly-fused rings. J. Am. Chem. Soc. 2012, 134, 20005−20008. (10) Chen, P.; Xu, T.; Dong, G. Divergent syntheses of fused βnaphthol and indene scaffolds by rhodium-catalyzed direct and decarbonylative alkyne-benzocyclobutenone couplings. Angew. Chem., Int. Ed. 2014, 53, 1674−1678. (11) Zeng, R.; Dong, G. Rh-Catalyzed Decarbonylative Coupling with Alkynes via C−C Activation of Isatins. J. Am. Chem. Soc. 2015, 137, 1408−1411. (12) Zeng, R.; Chen, P.; Dong, G. Efficient Benzimidazolidinone Synthesis via Rhodium-Catalyzed Double-Decarbonylative C-C Activation/Cycloaddition between Isatins and Isocyanates. ACS Catal. 2016, 6, 969−973. (13) Deng, L.; Xu, T.; Li, H.; Dong, G. Enantioselective Rhcatalyzed Carboacylation of C = N Bonds via C-C Activation of Benzocyclobutenones. J. Am. Chem. Soc. 2016, 138, 369−374. (14) Xia, Y.; Lu, G.; Liu, P.; Dong, G. Catalytic activation of carboncarbon bonds in cyclopentanones. Nature 2016, 539, 546−550. (15) Lei, Z.-Q.; Li, H.; Li, Y.; Zhang, X.-S.; Chen, K.; Wang, X.; Sun, J.; Shi, Z.-J. Extrusion of CO from aryl ketones: rhodium(I)-catalyzed C-C bond cleavage directed by a pyridine group. Angew. Chem., Int. Ed. 2012, 51, 2690−2694. (16) Wang, J.; Chen, W.; Zuo, S.; Liu, L.; Zhang, X.; Wang, J. Direct Exchange of a Ketone Methyl or Aryl Group to Another Aryl Group through C-C Bond Activation Assisted by Rhodium Chelation. Angew. Chem., Int. Ed. 2012, 51, 12334−12338. (17) Zhu, Z.; Li, X.; Chen, S.; Chen, P.; Billett, B. A.; Huang, Z.; Dong, G. Cobalt-Catalyzed Intramolecular Alkyne/Benzocyclobutenone Coupling: C-C Bond Cleavage via a Tetrahedral Dicobalt Intermediate. ACS Catal. 2018, 8, 845−849. (18) Suggs, J. W.; Jun, C.-H. J. Metal-catalysed alkyl ketone to ethyl ketone conversions in chelating ketones via carbon−carbon bond cleavage. J. Chem. Soc., Chem. Commun. 1985, 0, 92−93. (19) (a) Hoang, G. T.; Reddy, V. J.; Nguyen, H. H. K.; Douglas, C. J. Insertion of an Alkene into an Ester: Intramolecular OxyacylationReaction of Alkenes through Acyl C-O Bond Activation. Angew. Chem., Int. Ed. 2011, 50, 1882−1884. (b) Suggs, J. W.; Wovkulich, M. J.; Cox, S. D. Synthesis, Structure, and Ligand-Promoted Reductive Elimination in an Acylrhodium Ethyl Complex. Organometallics 1985, 4, 1101−1107.

G

DOI: 10.1021/acs.organomet.8b00309 Organometallics XXXX, XXX, XXX−XXX