Reactions with C-, N-, O-, and S-nucleophiles

Base-catalyzed hydrogen exchange, 16, 1 Basicity and acidity of azoles, 41, 187 Behavior of monocyclic 1,2,4-triazines in reactions with C-, N-, O-, and S-nucleophiles, 46, 73 1-, 2-, and 3-Benzazepines, 17, 45 Benzisothiazoles, 14, 43 38, 105 Benzisoxazoles, 8, 277 29, 1 Benzoazines, reactivity with nucleophiles,... 

Behavior of Monocyclic 1,2,4-Triazines in Reactions with C-, N-, O-, and S-Nucleophiles... 

Over the last few years, the Ir-catalyzed allylic substitution has been investigated in several laboratories and was found to be well suited for applications in organic synthesis. Using this reaction, branched chiral allylic derivatives can be prepared with high selectivity from simple achiral monosubstituted allylic substrates (Scheme 11.1). The reaction has been carried out with C, N, O, and S nucleophiles. The very broad range of nucleophiles is impressive. Several reviews have appeared on the subject [1]. At present, the best catalysts are prepared from [Ir(cod)Cl]2 (cod, cycloocta-1,5-diene) [2, 3] or [Ir(dbcot)Cl]2 (dbcot, dibenzocyclooctatetraene) [4] and a chiral phosphoramidite by base-induced C-H activation. Reliable experimental procedures have been developed for the reaction [5]. 

The reactions of a- and j8-aUyl epoxides, (5) and (6), have been investigated using O, N, C, and S nucleophiles under a wide variety of acidic and basic conditions." (g) Both epoxides undergo only anft-1,2-addition (an 5 2 ring opening at C(2) of the epoxide ring) with methanol under basic conditions, but give a mixture of the an/i-1,2-addition, the anft-l,4-addition, and the 5yn-1,4-addition products allylic... 

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