Kharasch-Sosnovsky Reaction:

Kharasch-Sosnovsky Reaction:

copper catalysed allylic oxidation using an organic peroxide.

reported by M. S. Kharasch and George Sosnovsky in 1958 ((DOI) DOI).

In the original publication the reactants are cyclohexene

and t-butyl perbenzoate with cuprous bromide and the

reaction product is cyclohex-1-en-3-yl benzoate:

 

Mechanism: (review: DOI). The reaction mechanism devised

by Beckwith et al (DOI) contains the following steps:

 

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[3,3]-sigmatropic rearrangement to transfer an allyl group to the imminium carbon

[3,3]-sigmatropic rearrangement to transfer an allyl group to the imminium carbon
REACTION MECHANISM
Starting point is to react the secondary amine with the aldehyde to form a cyclic imminium structure. Once generated, this is nicely set up to undergo a [3,3]-sigmatropic rearrangement to transfer an allyl group to the imminium carbon. The resulting formaldehyde imminium product is then hydrolyzed in the presence of water to afford the product plus an equivalent of formaldehyde





closer inspection, you can see that there is one less carbon in the product than the starting material. Furthermore, there are no reducing agents present, only acid (and presumably water)
 

ENZYMATIC DIELS ALDER REACTION

In a ground-breaking feat of protein engineering, US researchers have designed a synthetic enzyme that catalyses the Diels-Alder reaction - something that has not been seen in nature. The reaction is key to many organic syntheses and suggests that artificial enzymes could soon become part of the synthetic chemist's toolkit.

The Diels-Alder reaction - diene and dienophile undergo a pericyclic [4 + 2] cycloaddition to form a chiral cyclohexene ring. The image also shows the design target active site, with hydrogen bond acceptor and donor groups activating the diene and dienophile and a complementary binding pocket holding the two substrates in an orientation optimal for catalysis Science 16 July 2010:  Vol. 329 no. 5989 pp. 309-313  DOI: 10.1126/science.1190239 http://www.sciencemag.org/content/329/5989/309.abstract

Eugenol -------major volatile constituent of clove essential oil

Eugenol—From the Remote Maluku Islands to the International Market Place: A Review of a Remarkable and Versatile Molecule

Eugenol is a major volatile constituent of clove essential oil obtained through hydrodistillation of mainly Eugenia caryophyllata (=Syzygium aromaticum) buds and leaves. It is a remarkably versatile molecule incorporated as a functional ingredient in numerous products and has found application in the pharmaceutical, agricultural, fragrance, flavour, cosmetic and various other industries.

Guy P. Kamatou, Ilze Vermaak and Alvaro M. Viljoen

Department of Pharmaceutical Sciences, Faculty of Science, Tshwane University of Technology, Private Bag X680, Pretoria 0001, South Africa

read original article at

http://www.mdpi.com/1420-3049/17/6/6953

DR ANTHONY CRASTO

Ruthenium catalyst to carry out a cross coupling of an aryl amine with a phenyl boronate

Ruthenium-Catalyzed Carbon−Carbon Bond Formation via the Cleavage of an Unreactive Aryl Carbon−Nitrogen Bond in Aniline Derivatives with Organoboronates

Satoshi Ueno, Naoto Chatani, and FumitoshiKakiuchi

Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan, and Department of Applied Chemistry, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

J. Am. Chem. Soc., 2007, 129 (19), pp 6098–6099

http://pubs.acs.org/doi/abs/10.1021/ja0713431

 Ueno, Chatani and Kakiuchi used a ruthenium catalyst to carry out a cross coupling of an aryl amine with a phenyl boronate. What is remarkable is the fact that the transition metal did oxidative addition to an aryl-nitrogen bond

http://pubs.acs.org/doi/abs/10.1021/ja0713431

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THANKS AND REGARD'S
DR ANTHONY MELVIN CRASTO Ph.D

amcrasto@gmail.com

MOBILE-+91 9323115463

GLENMARK SCIENTIST , NAVIMUMBAI, INDIA
web link

http://amcrasto.bravehost.com/

http://anthonycrasto.jimdo.com/
http://www.anthonymelvincrasto.yolasite.com/ 

http://www.slidestaxx.com/anthony-melvin-crasto-phd 

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Source of anticancer agents---Broccoli

Broccoli as a source of anticancer agents

Most of the people are aware of healthy benefits of broccoli but the active constituents which makes broccoli to possess anticancer property may not be well known., The anticancer effect of Selenium (Se)-enriched broccoli will be highlighted according to the work done by researcher from Gunma University, Japan (Abdulah, et al.).

As a member of Se-accumulator Brassica family, broccoli accumulates Se-methylselenocysteine as the major Se compound when it is germinated in Se-enriched media. Therefore, Se-enriched broccoli accumulates two active anticancer agents: sulforaphane and Se-methylselenocysteine. The anticancer property of Sulforaphane, belonging to isothiocyanates and Se-methylselenocysteine has already been reported (Nishikawa, et. al, and Kim et. al. respectively).

Recently, broccoli sprouts have received considerable attention, because they contain ten times more sulforaphane than broccoli florets. Many studies have shown that both cruciferous vegetables and selenium may reduce the incidence of prostate cancer. 

References

1. Abdulah, R., Faried, A., Kobayashi, K., Yamazaki, C., Suradji, E. W., Ito, K., Suzuki, K., Murakami, M., Kuwano, H., Koyama, H. BMC Cancer, 2009, 9, 414.
2. Kim, T., Jung, U., Cho, D. Y., Chung, A.-S. Carcinogenesis, 2001, 22, 4, 559-565.
3. Nishikawa, T., Tsuno, N. H., Tsuchiya, T., Yoneyama, S., Yamada, J., Shuno, Y., Okaji, Y., Tanaka, J., Kitayama, J., Takahashi, K., Nagawa, H. Ann Surg Oncol. 2009, 16, 534–543.