References

Paper that our paper cites about our reaction’s chemistry:
Gonzalez, C. C.; Leon, E. I.; Riesco-Fagundo, C.; Suarez, E. Tetrahedron Lett. 2003, 44, 6347–6350.

This paper presents a method for the synthesis of 1-deoxy-1-halo-1-bromo-alditols with one carbon less than the original carbohydrate. This method involves the use of hypervalent heteroatoms to control radical halogenizations of methyl groups. These reactants are very electrophilic, and the bonds they form prevent certain sites from participating in radical reactions. Their purpose is analogous to the use protecting groups for carbonyl addition mechanisms. Suarez presents a set of ‘conditions’ for radical halogenization. These conditions are cited many times throughout the paper. Here, Suarez’s conditions are used with iodosobenzene diacetate. (Note that other periodinanes containing hypervalent iodine can be used as well.) Unfortunately, Suarez does not make any conclusions about the definite mechanisms for these transformations, because they are not known and never will be. Since radicals are so unpredictable and reactive, the mechanism proceeds slightly differently each time. Suarez does indicate that the reaction proceeds through a remote methyl oxidation—we have done that here. The carbon in the methyl group being halogenated forms a bond with an oxygen atom at some point during the reaction. Here is a picture of this mechanistic step that creates this bond:

Papers that cite this paper:
1) Oshima, K.; Yoshida, S. J. Organomet. Chem. 1999, 575, 1-20.
This paper outlines the synthesis of di-bromo compounds and the involvement of an organomanganese reagent as a facilitator in the process. Specifically, this research looks into the mechanism for the addition of a bromine atom, followed by the addition of another bromine atom to an organic molecule. Our molecule undergoes dibromonation to during the synthesis of an intermediate in the reaction.

2) Monrad, R. N.; Madsen, R. Tetrahedron 2011, 67, 8825-8850.
This paper also cites Suarez’s conditions, and it does it in almost an identical way to the way that our paper does.  Here, Suarez’s conditions are used to insert one iodine atom at an sp3 hybridized carbon in molecule 6.  Suarez’s conditions are incredibly powerful--they allow for complete control of a process that could theoretically halegonate any  C-H bond in these large molecules.

3) Ramesh, N. G.; Hassner, A. Eur. J. Org. Chem. 2005, 21, 1892-1902.
This paper cites Suarez’s article and a variety of articles focused on beta-fragmentation of alkoxy radicals.  This paper focuses mainly on the relationship between the methyl that is being halogenized and a hydroxyl group that located only a few bonds away.

 

Works Cited:

These are all the papers we consulted in making this website:

Abe, H.; Ito, Y.; Saneyoshi, H.; Abe, H. Hatano, K. Mashimo, T. Tetrahedron Lett. 2013, 54, 1080-1083.

Monrad, R. N.; Madsen, R. Tetrahedron 2011, 67, 8825-8850.

Gomberg, M. J. Am. Chem. Soc. 1900, 22, 757–771.

Gonzalez, C. C.; Leon, E. I.; Riesco-Fagundo, C.; Suarez, E. Tetrahedron Lett. 2003, 44, 6347–6350.

Oshima, K.; Yoshida, S. J. Organomet. Chem. 1999, 575, 1-20.

Ramesh, N. G.; Hassner, A. Eur. J. Org. Chem. 2005, 21, 1892-1902.

Rhodes, Gale. Crystallography Made Crystal Clear. Academic Press, San Diego, 1999

Shenvi, R. A.; Guerrero, C. A.; Shi, J.; Li, C.-C.; Baran, P. S. J. Am. Chem. Soc. 2008, 130, 7241-7243.

Shi, J.; Manolikakes, G.; Yeh C.-H.; Guerrero, C. A.; Shenvi, R. A.; Shigehisa, H.; Baran, P. S., J. Am. Chem. Soc. 2011, 133, 8014-8027.