Addition to double and triple bonds

For a review of the stereochemistry of electrophilic additions to double and triple bonds, see Fahey Top. Ster-eochem. 1948, 3. 237-342. For a review of the synthetic uses of stereoselective additions, sec Bartlett Tetrahedron 1980, 36. 2-72. pp. 3-15. 

Table 16.4 Group Rate Constants for HO Addition to Double and Triple Bonds at 298 K a...

Bach and coworkers [88] reported on intramolecular chloroamination reactions with FeCl2 as catalyst starting from 2-alkenyloxycarbonyl azides. TMSC1 was found to be an essential additive for the efficient addition to double and triple bonds. The corresponding oxazolidinones were obtained in moderate to high yields and with high diastereoselectivity (Scheme 3.14). 

Quantum-chemical calculations have been used to probe all the characteristic chemical reactions of CAs (at least in the case of silylenes and germylenes). The theoretical studies cover intramolecular rearrangements, insertions into 0-bonds, additions to double and triple bonds and dimerizations. Note that experimental data on the mechanisms of these reactions are still scarce and the results of theoretical studies are needed to understand the main trends in the reactivity of germylenes, stannylenes and plumbylenes. 

The most reliable data for hydroxyl radical additions to double and triple bonds have been collected in Table 41. It should be noted that, while no competition studies seem to have been made, the reactivity of... 

CH3S radical additions to double and triple bonds [153]... 

ALKYL RADICAL ADDITIONS TO DOUBLE AND TRIPLE BONDS... 

Chapter 1 deals with the kinetics of the dissociation of diatomic molecules and the recombination of atoms, and Chapters 2 and 3 with the reactions of atoms and radicals with molecules, abstraction (metathetical) processes and addition to double and triple bonds. Data for the reactions of metal atoms with a variety of inorganic, organic and metal organic compounds, derived from sodium flame and molecular beam techniques, are discussed in Chapter 4 and rapid substitution at labile metal ions in solution in Chapter 5. The theory of, and the experimental results for, ion-molecule reactions, i.e. chemical processes resulting from binary collisions of positive or negative ions with neutral molecules, are discussed in Chapter 6 and the reactions of solvated electrons in Chapter 7. 

The whole ensemble of unsaturated carbinols represents excellent starting materials for enantioselective 3,3-sigmatropic rearrangements and various kinds of intramolecular additions to double and triple bonds. 

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