Organic chemistry frontiers

M. J. S. Dewar and R. C. Dougherty, The PMO Theory of Organic Chemistry, Plenum Press, New brk, 1975. I. Fleming, Frontier Orbitals and Organic Chemical Reactions, Wiley-Interscience, New fark, 1976. 

The last decade has witnessed an unprecedented strengthening of the bone between theory and experiment in organic chemistry. Much of this success may be credited to the development of widely applicable, unifying concepts, such as the symmetry rules of Woodward and Hoffmann, and the frontier orbital thee>ry of Eukui. Whereas the the ore tical emphasis had historically been on detailed structure and spectroscopy, the new methods are de signe d to solve pre)blems e>f special importance to organic chemists reactivity, stereochemistry, and mechanisms. 

It is logical to discover Art more frequently at the frontier of science, where most innovation and creativity takes place. For organic synthesis, pharmaceutical research is on one of the frontiers. In pharmaceutical research laboratories, synthetic organic chemistry plays a major role in two departments, namely Medicinal... 

This volume is somewhat different from previous books on total synthesis. We have been fortunate enough to enlist eleven current practitioners in the field of total synthesis to describe one of their best total syntheses. These authors leveraged synthetic methodologies developed in their own laboratories as key operations in their construction of natural products. As such, this book reflects a true sense of what is happening at the frontiers of organic chemistry. 

Schneider H.J., Durr H. (eds.), Frontiers in Supramolecular Organic Chemistry and Photochemistry, VCH, Weinheim, 1991. 

Among the various methods proposed to produce selectively isolated enantiomers, the use of enantioselective catalysis is by far the most attractive one. The control of stereochemistry by use of a minute amount of an asymmetric catalyst offers clear advantages. Therefore, the design and development of catalytic enantioselective organic reactions is considered as one of the most attractive and challenging frontiers in synthetic organic chemistry. 

There is a vast amount of literature on self-assembly and/or self-organization, as this notion is used in practically all fields of science, from classic organic chemistry to polymer chemistry (Lindsey, 1991 Lawrence etah, 1995 Pope and Muller, 1991 Zeng and Zimmermaim, 1997), to the new frontiers of nano-technology, nanorobotics (Whitesides et al, 1991 Bissel et al., 1994 Whitesides and Boncheva,... 

Frontiers in Supramotecular Organic Chemistry and Photochemistry. Schneider, H.-J. Diirr, H.. Eds. VCH Weinheim, 1991. 

Murakami Y, Kikuchi J, Hisaeda Y, Ohno T (1991) in Schneider H-J, Durr H (eds) Frontiers in supramolecular organic chemistry and photochemistry. VCH, Weinheim, p 145... 

A. M. Braun and E. Oliveros, Local Concentrations Effects on Oxidation Reactions in Microheterogeneous Media, in Frontiers in Supramolecular Organic Chemistry and Photochemistry, H.-J. Schneider and H. Durr, Eds., VCH Verlagsgesellschaft, Weinheim, 1991, p. 393. 

Perfluoroalkyl groups adjacent to multiple bond systems lower the frontier molecular orbitals (FMOs) Therefore, cycloaddition reactions preferentially occur wrth electron-rich multiple-bond systems The preference of bis(trifluoromethyl)-substituted hetero-l,3-dienes for polar reactions makes them excellent model compounds for developing new types of diene reactions deviating from the well documented Diels-Alder scheme (pathway 1) A systematic study of the reactions of diene (l=2-3=4)-dienophile (5=6) combinations reveals new synthetic possibilities that have not yet been fully exploited as tools for preparative organic chemistry (equation 25)... 

Our understanding of organic chemistry has improved dramatically over the past few decades with the development of molecular orbital theory. In particular, the contributions of Woodward and Hoffmann have emphasised the importance of orbital symmetry in dictating the course of organic reactions. More recently, the symmetry properties of the orbitals close to the potential energy surface, the so-called frontier orbitals, have been shown to be of paramount importance. The basics of frontier orbital theory are... 

Although all his research applications are in the realm of ab initio electronic structure theory and computations, Rauk has taught the theory of structure and bonding from a frontier orbital point of view. He is the author of a graduate-level textbook on the orbital interaction theory of organic chemistry.208... 

A characteristic feature of [2 + 2] cycloaddition reactions is that the symmetry properties of the frontier orbitals of the reactants make them formally symmetry forbidden [4] through a symmetric pathway. As a result, the reactants must overcome an activation barrier which makes the process very slow for homogeneous reactants. In organic chemistry, photoexcitation can be used to change the nature of the frontier orbital occupation, breaking the 7r bond and hence facilitating the reaction, but otherwise high heat and other extreme conditions are required in order to make this type of reaction proceed. For reactions with silicon(lOO), chemisorption is observed to be facile for most alkenes even at room temperature [16], contrary to naive expectations based on the cycloaddition model. 

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