Fragmentation stereoelectronic requirements

A stereoelectronic requirement in radical addition to carbon-carbon double bonds first became apparent from studies on radical cyelization and the reverse (Fragmentation) reactions.54 56 It provides a rationalization for the preferential formation of the less thermodynamically stable exo-product (i.e. head addition) from the cyelization of to-alkcny] radicals (16 - Scheme 1.5). s 57 G4... 

A theoretical treatment of 1,2-oxathietane indicates planarity with aS-0 bond length of 1.669 A and a C-S-0 angle of 100.6°. The electronic spectrum was calculated. The character of the HOMO is largely that of the sulfur 3p orbital. A CNDO molecular orbital study of the retrocycloaddition of 1,2-oxathietane 2-oxide to sulfur dioxide and ethylene shows that strong heteroatom asymmetry lifts the stereoelectronic requirement that the thermal fragmentation occur by a suprafacial-antarafacial path. ... 

Figure 8.22 Divergent reactivity of the two diastereomeric azabicycles reflects stereoelectronic requirements to fragmentations.

In 1977, Trost published the first example of an asymmetric variant of the Tsuji-Trost reaction, termed the asymmetric allylic alkylation reaction (AAA). Much of the subsequent development of the AAA reaction can be attributed to the dedicated work of Trost and co-workers.There was a substantial time lag however, in the development of processes where high enantioselectivities were realized in a predictable fashion. This was due, in part, to the fact that chiral, asymmetrically pure ligands must create a chiral environment on the opposite face of the allyl fragment to the metal centre (a stereoelectronic requirement, vide infra)P This obviously represents a significant design challenge in the production of effective ligand systems. 

Several classes of such fragmentation reactions have been studied in detail in order to understand the effect of substituents, the stereoelectronic requirements, and the effects of the medium and of nucleophiles. The mesolytic fragmentation of bibenzyls with the reduction of the radical and nucleophilic trapping of the cation is the main process for stabilized fragments, typical examples being cumyl or benzhydryl (see Equation 4.12). The relative stability of radical and cation makes the cleavage selective for Ar Ar. " ... 

This so-called stereoelectronic factor operates to maximize or minimize orbital overlap, as the case requires, to obtain the most favorable energy. This was evident from the three- and four-center systems we have discussed by the VB and HMO methods. It was also implicit in favored anti-1,2-additions, 1,3-cyclizations (Fig. 23), fragmentations (e.g. (174)), etc. Here we have selected several reaction types to illustrate the principle. In this and other sections, we show that the tendency for reaction centers to be collinear or coplanar stems largely from orbital symmetry (bonding), but may also derive from steric and electrostatic effects, as well as PLM. 

Although this is the only chapter in which stereoelectronics appears in the title, you will soon recognize the similarity between the ideas we cover here and concepts like the stereospecificity of E2 elimination reactions (Chapter 19), the Karplus relationship (Chapter 32), the Felkin-Anh transition state (Chapter 33), and the conformational requirements for rearrangement (Chapter 37) and fragmentation (Chapter 38) reactions. 

These regioselectivities can be rationalized on the basis of stereoelectronic effects since it is assumed that colinearity between the scissible bond and the donating orbital (the ring it-orbital in the case of benzyl cation radicals, see Scheme 10) is required during fragmentation the reaction is faster for bonds... 

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