Catalyst-free multi-component cascade C–H-functionalization in water using molecular oxygen: an approach to 1,3-oxazines

 

Catalyst-free multi-component cascade C-H-functionalization in water using molecular oxygen: an approach to 1,3-oxazines

Green Chem., 2017, 19,4036-4042
DOI: 10.1039/C7GC01494E, Communication

Mohit L. Deb, Choitanya D. Pegu, Paran J. Borpatra, Prakash J. Saikia, Pranjal K. Baruah
Synthesis of 1,3-oxazines via catalyst free C-H functionalization using molecular oxygen in water.

Catalyst-free multi-component cascade C–H-functionalization in water using molecular oxygen: an approach to 1,3-oxazines

Mohit L. Deb,*^a  Choitanya D. Pegu,^a  Paran J. Borpatra,^a  Prakash J. Saikia^b  and  Pranjal K. Baruah*^a 

 Author affiliations

*Corresponding authors

^aDepartment of Applied Sciences, GUIST, Gauhati University, Guwahati-781014, India
E-mail: mohitdd.deb@gmail.com, baruah.pranjal@gmail.com
Fax: +91-8876998905
Tel: +91-8876998905

^bAnalytical chemistry division, CSIR-NEIST, Jorhat-785006, India

Abstract

Herein, catalyst-free 3-component reactions of naphthols, aldehydes, and tetrahydroisoquinolines to synthesize 1,3-oxazines is reported. The reaction is performed in H₂O in the presence of O₂ as the sole oxidant at 100 °C, which proceeds through the formation of 1-aminoalkyl-2-naphthols followed by selective α-C–H functionalization of tert-amine.

15-phenyl-7a,12,13,15-tetrahydronaphtho[1',2':5,6][1,3]oxazino[2,3- a]isoquinoline (4a):1
White solid; Yield 61 %, 221 mg;
1H NMR (500 MHz, CDCl3): δ 7.79-7.77 (m, 1H), 7.74 (d, J = 8.9 Hz, 1H), 7.43-7.41 (m, 1H), 7.33-7.28 (m, 8H), 7.24-7.19 (m, 3H), 7.11 (d, J = 8.9 Hz, 1H), 5.65 (s, 1H), 5.44 (s, 1H), 3.40-3.26 (m, 2H), 3.12-3.09 (m, 1H), 2.90- 2.86 (m, 1H);
13C NMR (125 MHz, CDCl3): δ 151.9, 142.3, 135.0, 133.0, 132.4, 129.3, 129.1, 128.9, 128.8 (2C), 128.7, 128.6, 128.2, 127.4, 126.5, 126.2, 123.1, 122.7, 118.9, 110.9, 82.2, 62.6, 45.4, 29.4;
HRMS (ESI) exact mass calculated for C26H21NO [M+H]+ : 364.1701; found: 364.1705.
The representative procedure for the synthesis of 4a is as follows: 2-naphthol (1a, 144 mg, 1 mmol), benzaldehyde (2a, 106 mg, 1 mmol), tetrahydroisoquinoline (3, 133 mg, 1 mmol) and water (1.5 mL) were added in a round-bottom flask equipped with a magnetic stirring bar and a reflux condenser. The whole apparatus was efficiently flushed with oxygen gas and then connected to a balloon filled with oxygen. After vigorous stirring at 100 oC for 12 h, water was removed under vacuum and purified the reaction mixture by column chromatography (100-200 mesh silica gel, hexane-ethyl acetate) to obtain the product 4a as white solid. The other 1,3-oxazines were synthesized and purified by following the procedure described above

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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