Cookson’s Dione

• 
  
• CAS No.: 2958-72-7
• Cookson's dione   
• Formula: C11H10O2
• Molecular Weight: 174.19600

Cookson’s Dione

125 W Batch Reaction
A solution of Diels Alder adduct 3[3] (2.61 g, 15 mmol) in degassed EtOAc (150 ml) was irradiated with a pre-warmed 125 W medium pressure mercury lamp in a 150 ml batch reactor equipped with a
Pyrex immersion well for 15 min. The solvent was removed in vacuo and chromatography on silica
(40% EtOAc in hexane to 100% EtOAc) yielded Cookson’s dione 4 as an off-white solid (2.38 g, 91%)


1.5 kW Flow Reaction
A solution of Diels Alder adduct 3 (436 g, 2.5 mol) in degassed EtOAc (0.5 M) was irradiated with the firefly reactor fitted with a Pyrex inner filter and lamp at 1.5 kW at 36 ml/min. The mixture was
concentrated in vacuo to a slurry to which was added hexane. The mixture was filtered, washing
with petroleum ether and the solid dried to give pure Cookson’s dione 4 as an off-white crystalline
solid (387 g, 89%): m.p. 242 - 243°C;

δH (400 MHz, CDCl3) 3.19 – 3.14 (2H, m, 2×CH), 2.95 – 2.90 (2H,m, 2×CH), 2.82 – 2.78 (2H, m, 2×CH), 2.72 – 2.68 (2H, m, 2×CH), 2.04 (1H, app. d, J = 11.4 Hz, CHH),
1.88 (1H, app. d, J = 11.4 Hz, CHH);

 δC (100 MHz, CDCl3) 212. 2 (2×C), 54.9 (2×CH), 44.8 (2×CH), 43.9 (2×CH), 40.6 (CH2), 38.9 (2×CH)

SMILES O=C2[C@@H]1[C@@H]3C[C@@H]4[C@H]1C(=O)[C@H]5[C@H]2[C@H]3[C@H]45

Palladium(0)-Catalyzed Methylcyclopropanation of Norbornenes with Vinyl Bromides and Mechanism Study

Jiangang Mao†‡, Hujun Xie§, and Weiliang Bao*†

† Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, P.R. China

‡ School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, P.R. China

§ School of Food Science and Biotechnology, Zhejiang Gongshang University, Hangzhou 310035, Zhejiang P.R. China

Org. Lett., 2015, 17 (15), pp 3678–3681

DOI: 10.1021/acs.orglett.5b01603

*E-mail: wlbao@zju.edu.cn.

Abstract

An unusual methylcyclopropanation from [2 + 1] cycloadditions of vinyl bromides to norbornenes catalyzed by Pd(OAc)2/PPh3 in the presence of CH3ONa and CH3OH has been established. A methylcyclopropane subunit was installed by a 3-fold domino procedure involving a key protonation course. Preliminary deuterium-labeling studies revealed that the proton came from methyl of CH3OH and also exposed an additional hydrogen/deuterium exchange process. These two proton-concerned reactions were fully chemoselective.

http://pubs.acs.org/doi/abs/10.1021/acs.orglett.5b01603

J. Mao, H. Xie, W. Bao, Org. Lett. 2015, 17, 3678 – 3681



Paper

http://www.mdpi.com/1420-3049/12/2/271/htm

Molecules 2007, 12(2), 271-282; doi:10.3390/12020271

Full Paper

Synthesis and Biological Evaluation of Rigid Polycyclic Derivatives of the Diels-Alder Adduct Tricyclo[6.2.1.02,7]undeca-4,9-dien-3,6-dione

Felicia Megumi Ito 1, Jacqueline Marques Petroni 1, Dênis Pires de Lima 1, Adilson Beatriz 1,*, Maria Rita Marques 2, Manoel Odorico de Moraes 3, Letícia Veras Costa-Lotufo 3, Raquel  Carvalho Montenegro 3, Hemerson Iury Ferreira Magalhães 3 and Cláudia do Ó Pessoa 3

1

Department of Chemistry, Federal University of Mato Grosso do Sul, Campo Grande, 

MS, Brazil,,

2

Department of Morphophysiology, Federal University of Mato Grosso do Sul, 

Campo Grande, MS, Brazil

3

Department of Physiology and Pharmacology, Federal University of Ceará, 

Fortaleza, CE, Brazil,,,

*

Author to whom correspondence should be addressed;

 Homepage: http://www.dqi.ufms.br/~lp4/adilson.htm.

1. Cookson, R.C.; Grundwell, E.; Hudec, J. Synthesis of cage-like molecules 
2. by irradiation of Diels-Alder adducts. Chem. Ind. (London) 1958, 1003–1004. [Google Scholar]

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