Palladium-catalyzed coupling of azoles with 1-aryltriazenes via C–H/C–N cleavage

 

Palladium-catalyzed coupling of azoles with 1-aryltriazenes via C–H/C–N cleavage

Wei-Can Daia  and  Zhong-Xia Wang*ab 

*Corresponding authors

aCAS Key Laboratory of Soft Matter Chemistry, Hefei National Laboratory for Physical Sciences at Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, P. R. China
E-mail: zxwang@ustc.edu.cn
Tel: +86 551 63603043

bCollaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, P. R. China

Abstract

In the presence of CuCl and ButOLi, PdCl2/dppe catalyzes the reaction of (benzo)oxazoles or (benzo)thiazoles with 1-aryltriazenes to yield arylated products of (benzo)oxazoles or (benzo)thiazoles. Functional groups including F, Cl, CF3, COOEt, CN, OMe, NMe2, Py, and thienyl groups can be tolerated.

Regioselective acylation and carboxylation of [60]fulleroindoline via electrochemical synthesis

    

3a (11.2 mg, 38%) were obtained along with unreacted 1 (1.1 mg, 4%).

1H NMR (400 MHz, CS2/CDCl3) δ 8.39 (d, J = 8.0 Hz, 2H), 7.60 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.7 Hz, 2H), 7.41 (d, J = 7.8 Hz, 1H), 7.29 (s, 1H), 7.04 (d, J = 7.8 Hz, 1H), 5.95 (s, 1H), 2.76 (s, 3H), 2.52 (s, 3H);

13C NMR (100 MHz, CS2/CDCl3, all 1C unless indicated) δ 196.06 (C=O), 167.78 (C=O), 152.39, 152.08, 151.38, 150.04, 149.83, 149.22, 148.81, 148.52, 148.26, 147.93, 147.86, 147.73, 147.36, 147.18, 147.14 (2C), 146.91, 146.86, 146.41, 146.40, 145.99 (2C), 145.95, 145.92, 145.53, 145.37, 145.33, 144.82 (2C), 144.80, 144.72, 144.54, 144.42, 144.31, 144.14, 143.84, 143.65, 143.42, 143.31, 143.05, 142.13, 141.93, 141.79, 141.72 (2C), 141.69, 141.55, 141.35, 141.24, 141.10, 140.63, 140.14, 139.93 (aryl C), 138.84, 137.70, 137.54 (aryl C), 137.47, 137.38, 135.44 (aryl C), 133.14 (aryl C), 129.16 (2C, aryl C), 128.72 (2C, aryl C), 128.61 (aryl C), 125.80 (aryl C), 125.42 (aryl C), 115.11 (aryl C), 83.58 (sp3 -C of C60), 69.89 (sp3 -C of C60), 62.42 (sp3 -C of C60), 56.81 (sp3 -C of C60), 26.84, 22.25;

UV-vis (CHCl3) λmax nm (log ε) 251.0 (5.1), 318.5 (4.6), 403.5 (4.0), 440.0 (3.9), 525.5 (3.2), 703.5 (2.5);

FT-IR ν/cm-1 (KBr) 2922, 2860, 1668, 1599, 1499, 1439, 1366, 1304, 1236, 1180, 1086, 1020, 964, 858, 802, 748, 691, 604, 528;

MALDI-TOF MS m/z calcd for C76H16NO2 [M+H]+ 974.1176, found 974.1165.

Regioselective acylation and carboxylation of [60]fulleroindoline via electrochemical synthesis

Hao-Sheng Lin,a  Yutaka Matsuo,a  Jun-Jie Wanga  and  Guan-Wu Wang*ab 

Author affiliations

Abstract

A regioselective and highly efficient electrochemical method for direct acylation and carboxylation of a [60]fulleroindoline has been developed. By using inexpensive and readily available acyl chlorides and chloroformates, both keto and ester groups can be easily attached onto the fullerene skeleton to afford 1,2,3,16-functionalized [60]fullerene derivatives regioselectively. In addition, a plausible mechanism for the formation of fullerenyl ketones and esters is proposed, and their further transformations under basic and acidic conditions have been investigated.

1,5-bis-(2-furanyl)-1,4-pentadien-3-one (FAF)

A catalytic aldol condensation system enables one pot conversion of biomass saccharides to biofuel intermediates

Huixiang Li,ab  Zhanwei Xu,a  Peifang Yana  and  Z. Conrad Zhang*a 

Author affiliations

*Corresponding authors

aState Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
E-mail: zczhang@yahoo.com

bDepartment of Chemical Engineering, University of Chinese Academy of Sciences, Beijing, China

Abstract

Producing bio-intermediates from lignocellulosic biomass with minimal process steps has a far-reaching impact on the biofuel industry. We studied the metal chloride catalyzed aldol condensation of furfural with acetone under conditions compatible with the upstream polysaccharide conversions to furfurals. In situ far infrared spectroscopy (FIR) was applied to guide the screening of aldol condensation catalysts based on the distinguishing characteristics of metal chlorides in their coordination chemistries with carbonyl-containing compounds. NiCl2, CoCl2, CrCl3, VCl3, FeCl3, and CuCl2 were selected as the potential catalysts in this study. The FIR results further helped to rationalize the excellent catalytic performance of VCl3 in furfural condensation with acetone, with 94.7% yield of biofuel intermediates (C8, C13) in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) solvent. Remarkably, addition of ethanol facilitated the acetal pathway of the condensation reaction, which dramatically increased the desired product selectivity over the furfural pathway. Most significantly, we demonstrate for the first time that VCl3 catalyzed aldol condensation in acidic medium is fully compatible with upstream polysaccharide hydrolysis to monosaccharide and the subsequent monosaccharide isomerization and dehydration to furfurals. Our preliminary results showed that a 44% yield of biofuel intermediates (C8, C13) can be obtained in one-pot conversion of xylose catalyzed by paired metal chlorides, CrCl2 and VCl3. A number of prior works have shown that the biofuel intermediates derived from the one-pot reaction of this work can be readily hydrogenated to biofuels.

1,5-bis-(2-furanyl)-1,4-pentadien-3-one (FAF)

FAF is a yellow solid.1H NMR (400 MHz, CDCl3, TMS) δ 7.51 – 7.46 (m, 4H), 6.92 (d, J = 15.6 Hz, 2H), 6.69 (d, J = 3.4 Hz, 2H), 6.50 – 6.49 (m, 2H);13C NMR (100 MHz, CDCl3) δ 188.1, 151.6, 144.9, 129.2, 123.2, 115.8, 112.6

Synthesis of β-keto sulfones via a multicomponent reaction through sulfonylation and decarboxylation

 

1-Phenyl-2-(phenylsulfonyl)ethan-1-one (2a) 1

1H NMR (400 MHz, CDCl3) δ 7.92 (m, 4H), 7.70 – 7.58 (m, 2H), 7.54 (t, J = 7.6 Hz, 2H), 7.48 (t, J = 7.3 Hz, 2H), 4.74 (s, 2H).

13C NMR (101 MHz, CDCl3) δ 187.9, 138.7, 135.7, 134.4, 134.2, 129.3, 129.2, 128.9, 128.6, 63.4.

References 1. Lu, Q.; Zhang, J.; Peng, P.; Zhang, G.; Huang, Z.; Yi, H.; Millercd, T. J.; Lei, A. Chem. Sci. 2015, 6, 4851.

Synthesis of β-keto sulfones via a multicomponent reaction through sulfonylation and decarboxylation

Jiyao Yu,b  Runyu Mao,a  Qingyu Wanga  and  Jie Wu*ac 

*Corresponding authors

aDepartment of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, China
E-mail: jie_wu@fudan.edu.cn

bSchool of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Drive, Atlanta, USA

cState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China

Abstract

A copper(I)-catalyzed synthesis of β-keto sulfones through a multicomponent reaction of aryldiazonium tetrafluoroborates, 3-arylpropiolic acids, sulfur dioxide, and water was developed. This reaction proceeds through a tandem radical process, and the sulfonyl radical, generated from the combination of aryldiazonium tetrafluoroborates with DABCO·(SO2)2, acts as the key intermediate. The transformation involves sulfonylation and decarboxylation, which allows for the efficient synthesis of the desired β-keto sulfones.

 

Nanoscale graphene oxide sheets (NGO), as activated carbocatalysts, were synthesized by a reduction size strategy and used in chemoselective oxidative conversion of benzylic C–H to the corresponding carboxylic acid. On the basis of the results of the optimization process of different parameters, 3 equiv of H2O2 for each C–H group, 100 wt % of NGO in aqueous medium, acetone as a cosolvent, and a reaction temperature of 100 °C were selected as optimum parameters.

In this optimum condition, xylenes and toluene over 24 h with good yield were converted to the corresponding carboxylic acid, and in the case of diphenylmethane and ethylbenzene, these substrates with excellent yield were converted to benzophenone and acetophenone.

Selective Oxidation of Benzylic C–H Using Nanoscale Graphene Oxide as Highly Efficient Carbocatalyst: Direct Synthesis of Terephthalic Acid

Masoud Heidari, Alireza Sedrpoushan* , and Farajollah Mohannazadeh

Institute of Industrial Chemistry, Iranian Research Organization for Science and Technology (IROST), P.O. Box 33535-111, Tehran, Iran

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00056

http://pubs.acs.org/doi/full/10.1021/acs.oprd.7b00056

 

*Tel.: +98 21 56276031. E-mail address: sedrpoushan1395@gmail.com (Alireza Sedrpoushan).

 

  

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2-{[6-Chloro-3-methyl-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl]methyl}-4-fluorobenzonitrile

2-{[6-Chloro-3-methyl-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl]methyl}-4-fluorobenzonitrile (4)

white solid . Mp: 193–195 °C.

 

1H NMR (400 MHz, CDCl3) δ (ppm): 7.74–7.76(m, 1H), 7.14–7.17 (m, 1H), 6.95–6.97 (m, 1H), 6.05 (s, 1H), 5.51 (s, 2H), 3.40 (s, 3H).

2-({3-Methyl-6-[(3R)-3-piperidinylamino]-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl}methyl)-4-fluorobenzonitrile

 

2-({3-Methyl-6-[(3R)-3-piperidinylamino]-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl}methyl)-4-fluorobenzonitrile (8)

Mp: 90 °C decomposed.

 

1H NMR (400 MHz, CD3OD) δ (ppm): 7.85–7.89 (m, 1H), 7.25–7.28 (m, 1H), 6.96–6.99 (m, 1H), 5.37–5.51 (m, 2H), 4.84 (s, 1H), 3.42–3.49 (m, 1H), 3.28 (s, 3H), 3.11–3.15 (m, 1H), 2.89–2.93 (m, 1H), 2.46–2.58 (m, 2H), 1.92–1.95 (m, 1H), 1.48–1.70 (m, 3H).

 

MS (ESI+): m/z, 358.06 ([M + H]+).

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