2,5-Diformylfuran an easy molecule to learn NMR

2,5-Diformylfuran (DFF), 5 (lit. 2 ) 2 Kashparova, V. P., Khokhlova, E. A., Galkin, K. I., Chernyshev, V. M. & Ananikov, V. P. The “onepot” synthesis of 2,5-diformylfuran, a promising synthon for organic materials in the conversion of biomass. Russ. Chem. Bull. 64, 1069-1073 (2015).

1H NMR (CDCl3) = 9.87 (s, 2H), 7.35 (s, 2H);

13C NMR (CDCl3) = 181.1, 154.1, 122.5 ppm.

PREDICT

Efficient route for the construction of polycyclic systems from bioderived HMF 

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC02211E, Paper

F. A. Kucherov, K. I. Galkin, E. G. Gordeev, V. P. Ananikov
Efficient one-pot synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described using a [4 + 2] cycloaddition reaction.

Efficient route for the construction of polycyclic systems from bioderived HMF

F. A. Kucherov,^a  K. I. Galkin,^a  E. G. Gordeev^a  and  V. P. Ananikov*^a 

 Author affiliations

*Corresponding authors

^aZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, Russia
E-mail: val@ioc.ac.ru
Web: http://AnanikovLab.ru

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A convenient transformation of phenols into the corresponding aryl fluorosulfates is presented: the first protocol to completely circumvent direct handling of gaseous sulfuryl fluoride (SO2F2). The proposed method employs 1,1′-sulfonyldiimidazole as a precursor to generate near-stoichiometric amounts of SO2F2 gas using a two-chamber reactor. With NMR studies, it was shown that this ex situ gas evolution is extremely rapid, and a variety of phenols and hydroxylated heteroarenes were fluorosulfated in good to excellent yields.

Ex Situ Generation of Sulfuryl Fluoride for the Synthesis of Aryl Fluorosulfates

Cedrick Veryser‡ , Joachim Demaerel‡, Vidmantas Bieliu̅nas, Philippe Gilles, and Wim M. De Borggraeve* 

Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium

Org. Lett., Article ASAP

DOI: 10.1021/acs.orglett.7b02522

*E-mail: wim.deborggraeve@kuleuven.be.

http://pubs.acs.org/doi/abs/10.1021/acs.orglett.7b02522?utm_content=bufferd3ad9&utm_medium=social&utm_source=twitter.com&utm_campaign=buffer

4-fluoro-[1,1'-biphenyl]-4-yl sulfurofluoridate (compound 1) 

General procedure A was followed using 192 mg of 4-fluoro-4’-hydroxybiphenyl (98 wt%, 1.0 mmol, 1.0 eq.). The crude reaction mixture was purified by solid-phase flash column chromatography on silicagel (heptane, 100%). The title compound was obtained as a white solid (258 mg, 96%). Rf = 0.39 (heptane/ethyl acetate, 9/1). Melting point = 47 – 49 °C.

1 H NMR (400 MHz, CDCl3): 7.62 (d, J = 8.5 Hz, 1H), 7.52 (dd, J = 8.1, 5.5 Hz, 1H), 7.41 (d, J = 8.5 Hz, 1H), 7.16 (t, J = 8.5 Hz, 1H). 

13C NMR (101 MHz, CDCl3): δ 163.05 (d, J = 247.9 Hz), 149.51, 141.17, 135.55 (d, J = 3.3 Hz), 129.06, 128.98, 121.42, 116.13 (d, J = 21.6 Hz).

19F NMR (376 MHz, CDCl3): δ 37.18, -114.68 (m).

 IR (neat) cm-1 : 1437, 1232, 921, 815. 

CHN: calculated for C12H8F2O3S: C 53.33%, H 2.98%, N 0.00%; found: C 53.43%, H 3.26%, N 0.00%.

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2,5-Bis(morpholinomethyl)furan

2,5-Bis(morpholinomethyl)furan, 11

Yield 98%, 1H NMR (CDCl3) = 6.13 (s, 2H), 3.70 (m, 8H), 3.51 (s, 4H), 2.45 (m, 8H);

13C NMR (CDCl3) = 150.9, 109.7, 66.8, 55.3, 53.2 ppm.

 m/z HRMS (ESI) Calcd. for C14H22N2O3 [M+H]: 267.1703. Found 267.1703.

Efficient route for the construction of polycyclic systems from bioderived HMF 

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC02211E, Paper

F. A. Kucherov, K. I. Galkin, E. G. Gordeev, V. P. Ananikov
Efficient one-pot synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described using a [4 + 2] cycloaddition reaction.

Efficient route for the construction of polycyclic systems from bioderived HMF

F. A. Kucherov,^a  K. I. Galkin,^a  E. G. Gordeev^a  and  V. P. Ananikov*^a 

 Author affiliations

*Corresponding authors

^aZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, Russia
E-mail: val@ioc.ac.ru
Web: http://AnanikovLab.ru

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Endo-4,7-bis(hydroxymethyl)hexahydro-1H-4,7-epoxyisoindole-1,3(2H)-dione (endo-4,7- bis(hydroxymethyl)norcantharimide)

Endo-4,7-bis(hydroxymethyl)hexahydro-1H-4,7-epoxyisoindole-1,3(2H)-dione (endo-4,7- bis(hydroxymethyl)norcantharimide), 4 (method A)

Endo-4,7-bis(hydroxymethyl)norcantharimid-5-ene (120 mg, 0.53 mmol) was dissolved in water (3 mL), Pd/C 10% was added (15 mg) and reaction mixture was placed under hydrogen atmosphere for 8 h at 24 °C. Catalyst was filtered off and washed thoroughly with water (3 × 3 mL), filtrate was evaporated under reduced pressure. Target compound 4 was obtained as white solid, yield 87% (110 mg).

1H NMR (D2O) = 3.76 (s, 4H), 3.46 (s, 2H), 1.61-1.72 (m, 4H);

1H NMR (DMSO-d6) = 11.10 (s, 1H), 5.08 (s, 2H), 3.66 (s, 4H), 3.37 (s, 2H), 1.71 (m, 2H), 1.49 (m, 2H);

13C NMR (D2O) = 179.0, 88.8, 60.7, 52.3, 27.0 ppm.

m/z HRMS (ESI) Calcd. for C10H13NO5 [M+Na]: 250.0686. Found 250.0696.

Efficient route for the construction of polycyclic systems from bioderived HMF 

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC02211E, Paper

F. A. Kucherov, K. I. Galkin, E. G. Gordeev, V. P. Ananikov
Efficient one-pot synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described using a [4 + 2] cycloaddition reaction.

Efficient route for the construction of polycyclic systems from bioderived HMF

F. A. Kucherov,^a  K. I. Galkin,^a  E. G. Gordeev^a  and  V. P. Ananikov*^a 

 Author affiliations

*Corresponding authors

^aZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, Russia
E-mail: val@ioc.ac.ru
Web: http://AnanikovLab.ru

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2,5-Bis(ethoxymethyl)furan

2,5-Bis(ethoxymethyl)furan, 6

1H NMR (CDCl3) = 6.20 (s, 2H), 4.36 (s, 4H), 3.47 (q, 4H, J = 7.1 Hz), 1.16 (t, 6H, J = 7.1 Hz);


13C NMR (CDCl3) = 150.9, 109.7, 65.7, 64.7, 15.1 ppm

PREDICTS

Efficient route for the construction of polycyclic systems from bioderived HMF 

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC02211E, Paper

F. A. Kucherov, K. I. Galkin, E. G. Gordeev, V. P. Ananikov
Efficient one-pot synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described using a [4 + 2] cycloaddition reaction.

Efficient route for the construction of polycyclic systems from bioderived HMF

F. A. Kucherov,^a  K. I. Galkin,^a  E. G. Gordeev^a  and  V. P. Ananikov*^a 

 Author affiliations

*Corresponding authors

^aZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, Russia
E-mail: val@ioc.ac.ru
Web: http://AnanikovLab.ru

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Efficient route for the construction of polycyclic systems from bioderived HMF

 

Efficient route for the construction of polycyclic systems from bioderived HMF

 

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC02211E, Paper

F. A. Kucherov, K. I. Galkin, E. G. Gordeev, V. P. Ananikov
Efficient one-pot synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described using a [4 + 2] cycloaddition reaction.

Efficient route for the construction of polycyclic systems from bioderived HMF

F. A. Kucherov,^a  K. I. Galkin,^a  E. G. Gordeev^a  and  V. P. Ananikov*^a 

 Author affiliations

*Corresponding authors

^aZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, Russia
E-mail: val@ioc.ac.ru
Web: http://AnanikovLab.ru

Abstract

The first synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described. The Diels–Alder reaction was used to implement the transition from HMF to a non-planar framework, which possessed structural cores of naturally occurring biologically active compounds and building blocks of advanced materials. A one-pot, three-step sustainable synthesis in water was developed starting directly from HMF. The reduction of HMF led to 2,5-bis(hydroxymethyl)furan (BHMF), which could be readily involved in the Diels–Alder cycloaddition reaction with HMF-derived maleimide, followed by hydrogenation of the double bond. The described transformation was diastereoselective and proceeded with a good overall yield. The applicability of the chosen approach for the synthesis of analogous structures containing amine functionality on the side chain was demonstrated. To produce the target compounds, only platform chemicals were used with carbohydrate biomass as the single carbon source.

Endo-4,7-bis(hydroxymethyl)-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindole-1,3(2H)-dione (endo-4,7-bis(hydroxymethyl)norcantharimid-5-ene), 3

1H NMR (DMSO-d6) = 10.82 (s, 1H), 6.37 (s, 2H), 5.11 (t, 2H, J = 5.7 Hz), 3.97 (dd, 2H, J = 5.7 Hz, 12.8 Hz), 3.84 (dd, 2H, J = 5.7 Hz, 12.8 Hz), 3.44 (s, 2H);
13C NMR (DMSO-d6) = 176.9, 136.0, 92.1, 59.8, 48.8 ppm.
m/z HRMS (ESI) Calcd. for C10H11NO5 [M+Na]: 248.0529. Found 248.0536.

 

1H NMR PREDICT

 

13C NMR PREDICT

 

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O=C1NC(=O)[C@H]3[C@@H]1[C@]2(C=C[C@]3(CO)O2)CO

Metal-free oxidative cyclization of 2-aminobenzothiazoles and cyclic ketones enabled by the combination of elemental sulfur and oxygen

Metal-free oxidative cyclization of 2-aminobenzothiazoles and cyclic ketones enabled by the combination of elemental sulfur and oxygen

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC02014G, Communication

Yanjun Xie, Xiangui Chen, Zhen Wang, Huawen Huang, Bing Yi, Guo-Jun Deng
Aerobic cyclization of 2-aminobenzothiazoles and cyclic ketones enabled by the combination of elemental sulfur and oxygen under metal-free conditions.

Metal-free oxidative cyclization of 2-aminobenzothiazoles and cyclic ketones enabled by the combination of elemental sulfur and oxygen

Yanjun Xie,^ab  Xiangui Chen,^a  Zhen Wang,^a  Huawen Huang,*^a  Bing Yi*^b  and  Guo-Jun Deng*^a 

*Corresponding authors

^aKey Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, China
E-mail: hwhuang@xtu.edu.cn, gjdeng@xtu.edu.cn
Fax: (+86)0731-5829-2251
Tel: (+86)0731-5829-8601

^bCollege of Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiangtan 411104, China
E-mail: bingyi2004@126.com

http://pubs.rsc.org/en/Content/ArticleLanding/2017/GC/C7GC02014G?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Abstract

Metal-free oxidative cyclization for the one-pot synthesis of benzo[d]imidazo[2,1-b]thiazoles from 2-aminobenzothiazoles and cyclic ketones is described. Elemental sulfur combined with molecular oxygen as the benign co-oxidant was found to be unique and highly effective to promote this transformation without the aid of any metal salts. Various cyclic ketones smoothly reacted with 2-aminobenzothiazoles to give functional benzo[d]imidazo[2,1-b]thiazoles in good to very high yields, which thereby demonstrated the synthetic convergence of this methodology.

 

 

7,8,9,10-Tetrahydrobenzo[d]benzo[4,5]imidazo[2,1-b]thiazole (3a)

White solid; yield: 39.2 mg (86%), mp 140-142 °C.

 

1H NMR (400 MHz, CDCl3, ppm) δ 7.67-7.62 (m, 2H), 7.38 (t, J = 7.76 Hz, 1H), 7.27 (t, J = 7.68 Hz, 1H), 3.07-3.04 (m, 2H), 2.77-2.74 (m, 2H), 2.00-1.95 (m, 2H), 1.92-1.86 (m, 2H);

 

13C NMR (100 MHz, CDCl3, ppm) δ 145.1, 142.4, 132.9, 129.7, 125.5, 123.9, 123.5, 121.8, 111.9, 24.8, 22.8, 22.7, 21.8;

 

MS (EI) m/z (%) 228, 200 (100), 160, 108, 51;

 

HRMS calcd. for: C13H13N2S + (M+H)+ 229.07940, found 229.07941.

 

 

 

 

 

PREDICT

 

 

cas 325766-28-7

C₁₃ H₁₂ N₂ S, 228.31,  Benzimidazo[2,​1-​b]​benzothiazole, 7,​8,​9,​10-​tetrahydro-

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C1CCCc2c1nc3sc4ccccc4n23