2H-1,3-Benzoxazine natural products and related bioactive molecules.

4-(2-Bromo-5-chlorobenzyl)-7-chloro-2-phenyl-2H-benzo[e][1,3]oxazine 2 as a light-yellow solid (82% yield).

1H NMR (500 MHz, CDCl3): δ (ppm) 7.55–7.52 (m, 3H), 7.42–7.34 (m, 3H), 7.30 (d, 1H, J = 3.5 Hz,) 7.29 (s, 1H), 7.12 (dd, 1H, J = 8.5 Hz, 2.5 Hz), 6.95–6.91 (m, 2H), 6.57 (1H, s), 4.16 (ABq, 2H, ΔδAB = 0.05, JAB = 16.5 Hz).

13C NMR (125 MHz, CDCl3): δ (ppm) 161.5, 155.8, 139.2, 138.9, 138.1, 133.8, 133.5, 130.6, 128.8, 128.7, 128.5, 127.0, 126.3, 122.6, 121.9, 117.3, 116.2, 88.9, 40.8.

HRMS TOF MS (m/z): [M + H]+ calcd for [C21H14BrCl2NO H] 445.9709; found 445.9713.

FTIR(neat): 3060, 1633, 1596, 1454, 1364, 1344 cm–1.

Spectroscopic data for 2 were identical to those reported in the literature.(4)

Li, H.; Belyk, K. M.; Yin, J.; Chen, Q.; Hyde, A.; Ji, Y.; Oliver, S.; Tudge, M.; Campeau, L.-C.; Campos, K. R. J. Am. Chem. Soc. 2015, 137,13728– 13731 DOI: 10.1021/jacs.5b05934

Development of a General Protocol To Prepare 2H-1,3-Benzoxazine Derivatives

Ji Qi*†∥ , Steven F. Oliver‡∥, Wensong Xiao§, Licheng Song§, and Karel M. J. Brands∥

† Department of Process Research and Development, MSD R&D (China) Co., Ltd., Building 21 Rongda Road, Wangjing R&D Base, Zhongguancun Electronic Zone West Zone, Beijing 100012, China

‡ Department of Process Research and Development, Merck Sharp & Dohme, Hertford Road, Hoddesdon, Hertfordshire EN11 9BU, United Kingdom

§ Department of Synthetic Chemistry, Pharmaron Beijing Co., Ltd., 6 Taihe Road BDA, Beijing, 100176, China

∥ Department of Process Research and Development, Merck Research Laboratories, P.O. Box 2000, Rahway, New Jersey 07065, United States

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00209

Publication Date (Web): August 23, 2017

Copyright © 2017 American Chemical Society

*E-mail: ji_qi@merck.com.

ACS Editors’ Choice – This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

Abstract

A practical synthesis and detailed development process of 2H-1,3-benzoxazine derivatives catalyzed by aldimine and trifluoromethanesulfonic acid is described. A broad range of substrates with diverse steric and electronic properties were explored. Aliphatic/aromatic/heteroaromatic substrates all proceed well under conditions which have been optimized into a robust, scalable process.

http://pubs.acs.org/doi/full/10.1021/acs.oprd.7b00209

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Photochemical intramolecular amination for the synthesis of heterocycles

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC02261A, Communication

Shawn Parisien-Collette, Corentin Cruche, Xavier Abel-Snape, Shawn K. Collins
Polycyclic heterocycles can be formed in good to excellent yields via photochemical conversion of the corresponding substituted aryl azides under irradiation with purple LEDs in a continuous flow reactor.

Photochemical intramolecular amination for the synthesis of heterocycles

 

Shawn Parisien-Collette,^a  Corentin Cruché,^a  Xavier Abel-Snape^a  and  Shawn K. Collins*^a 

 Author affiliations

*Corresponding authors

^aShawn Parisien-Collette, Corentin Cruché, Xavier Abel-Snape and Prof, Dr Shawn K. Collins, Department of Chemistry and Centre in Green Chemistry and Catalysis, Université de Montréal, CP 6128 Station Downtown, Montréal, Canada H3C 3J7
E-mail: shawn.collins@umontreal.ca

Abstract

Polycyclic heterocycles can be formed in good to excellent yields via photochemical conversion of the corresponding substituted aryl azides under irradiation with purple LEDs in a continuous flow reactor. The experimental set-up is tolerant to UV-sensitive functional groups while affording diverse carbazoles, as well as an indole and pyrrole framework, in short reaction times. The photochemical method is presumed to progress through a mechanism differing from the other methods of azide activation involving transition metal catalysis.

Methyl 9H-carbazole-2-carboxylate (9): Following the Photodecomposition Procedure A, starting from Methyl 2’-azido-[1,1’-biphenyl]-4-carboxylate, the crude mixture was purified by silica gel column chromatography (100 % hexanes → 10 % ethyl acetate in hexanes), to afford the desired product as a white solid (24.3 mg, 72 % yield). Following the Photodecomposition Procedure B, starting from Methyl 2’-azido-[1,1’- biphenyl]-4-carboxylate, the crude mixture was purified by silica gel column chromatography (100 % hexanes → 10 % ethyl acetate in hexanes), to afford the desired product as a white solid (27.7 mg, 82 % yield). NMR data was in accordance with what was previously reported.16
16 Takamatsu, K.; Hirano, K.; Satoh, T.; Miura, M. Org. Lett. 2014, 16, 2892-2895

NEXT..............

 

4-Isopropyl-9H-carbazole (14): Following the Photodecomposition Procedure A, starting from 2-azido-2’-isopropyl-1,1’-biphenyl, the crude mixture was purified by silica gel column chromatography (100 % hexanes → 10 % ethyl acetate in hexanes), to afford the desired product as a yellow solid (16.6 mg, 53 % yield). Following the Photodecomposition Procedure B, starting from 2-azido-2’-isopropyl-1,1’-biphenyl and using ethyl acetate as the solvant, the crude mixture was purified by silica gel column chromatography (100 % hexanes → 10 % ethyl acetate in hexanes), to afford the desired product as a yellow solid (16.0 mg, 51 % yield).

1H NMR (400 MHz, DMSO-d6) δ = 11.29 (s, 1H), 8.11 (d, J = 8.1 Hz, 1H), 7.50 (d, J = 8.1 Hz, 1H), 7.39-7.31 (m, 3H), 7.19- 7.15 (m, 1H), 7.08-7.03 (m, 1H), 3.92-3.82 (m, 1H), 1.41 (d, J = 6.8 Hz, 6H);

13C NMR (100 MHz, DMSO-d6) δ = 143.9, 140.3, 140.1, 126.0, 125.2, 122.8, 122.2, 119.9, 119.1, 114.9, 111.2, 108.9, 30.2, 22.8 (2C);

HRMS (ESI) m/z calculated for C15H15N [M-H]- 208.1130; found 208.1126.

///////////http://pubs.rsc.org/en/Content/ArticleLanding/2017/GC/C7GC02261A?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Diethyl Chlorophosphate

 

 

Diethyl Chlorophosphate (CAS no 814–49–3)(15)

Preparative Procedure

In a dry four-neck 250 mL round-bottom flask equipped with a mechanical stirrer, a thermometer, and an argon inlet were introduced at 20 °C triethylamine (21.3 g, 210 mmol), tert-butyl methyl ether (75 mL), and ethanol (9.67 g, 210 mmol). Phosphorus oxychloride (15.3 g, 100 mmol) was added dropwise in 10 min via a syringe; the temperature was maintained below −5 °C. Then, the cooling bath was removed and the white suspension was vigorously stirred during 5 h at 20 °C. The mixture was filtered and the solid was rinsed with 3 × 100 mL of diethyl ether. The solvents were removed under vacuo. The resulting crudez product was distilled under reduced pressure to afford 15.4 g (89% yield) of diethyl chlorophosphate containing 3% of triethylphosphate.

Eb3 = 51 °C (lit:(3) Eb10 = 85–87 °C).

 

1H NMR (CDCl3, 300 MHz, δ): 1.37 (6H, t, J = 6.0 Hz), 4.16–4.30 (4H, m).

 

13C NMR (CDCl3, 75 MHz, δ): 15.6 (d, J = 7.5 Hz), 65.7 (d, J = 6.8 Hz).

 

 

31P RMN (CDCl3, 121 MHz, δ): 4.5.

 

15Acharya, J.; Gupta, A. K.; Shakya, P. D.; Kaushik, M. P. Tetrahedron Lett. 2005, 46, 5293 DOI: 10.1016/j.tetlet.2005.06.024

 

  

 

 

Eco-Friendly and Industrially Scalable Synthesis of the Sex Pheromone of Lobesia botrana. Important Progress for the Eco-Protection of Vineyard

Gérard Cahiez*† , Olivier Guerret‡, Alban Moyeux†§, Samuel Dufour‡, and Nicolas Lefevre†

† Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris (IRCP), F-75005 Paris, France

‡ M2i, Route Nationale 117, Lotissement Induslacq, 64170 Lacq, France

§ Université Paris 13, 74 rue Marcel Cachin, 93017 Bobigny, France

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00206

 

*E-mail: gerard-cahiez@chimie-paristech.fr.

http://pubs.acs.org/doi/suppl/10.1021/acs.oprd.7b00206

 

//////////////http://pubs.acs.org/doi/suppl/10.1021/acs.oprd.7b00206/suppl_file/op7b00206_si_001.pdf

 

 

 

 

 

 

 

http://www.rsc.org/suppdata/c6/nj/c6nj03712g/c6nj03712g1.pdf

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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