Rhodium catalysts insertion into allylic

For the aziridination of 1,3-dienes, copper catalysis gave better yields of A-tosyl-2-alkenyl aziridines with 1,3-cyclooctadiene, 1,4-addition occurred exclusively (50%) [46]. Good results were also obtained on rhodium catalysed decomposition of PhI=NNs (Ns = p-nitrophenylsulphonyl) with some alkenes the aziridination was stereospecific, whereas with chiral catalysts asymmetric induction (up to 73% ee) was achieved. However, cyclohexene gave predominantly (70%) a product derived from nitrene insertion into an allylic carbon-hydrogen bond [47]. 

Carbene complexes, generated by the reaction between metal salts and diazo compounds can insert into C-H bonds in a form of CH activation (see Chapter 3 for other CH activation reactions). While early reactions involved the use of copper salts as catalysts (Schemes 8.143 and 8.144), rhodium complexes are now more widely used. In molecules such as cyclohexane, there is no issue of regioselectivity, but this issue is critical for the use of the reaction in synthesis. Both steric and electronic factors influence selectivity. Carbon atoms where a build up of some positive charge can be stabilized are favoured. Hence, allylic positions and positions a- to a heteroatom such as oxygen or nitrogen, are favoured. The reaction at tertiary C-H bonds, rather than primary C-H bonds is also favoured for the same reason, but, in this case, are also disfavoured by steric effects. Reactivity and selectivity are also influenced by both the structure of the catalyst, and the... 

In the presence of a rhodium catalyst, when the enyne eontains an halogen atom in allylic position, the allylic activation appears to take place first and the triple bond then inserts into the metal-halogen bond to form the eyelic diene 31 with halogen migration (Scheme 6) [22]. 

Rhodium complexes generated from A-functionalized (S)-proline 3.60 [933, 934, 935] or from methyl 2-pyrrolidone-5-carboxylates 3.61 [936, 937, 938] catalyze the cyclopropanation of alkenes by diazoesters or -ketones. Diastereoisomeric mixtures of Z- and E-cydopropylesters or -ketones are usually formed, but only the Z-esters exhibit an interesting enantioselectivity. However, if intramolecular cyclopropanation of allyl diazoacetates is performed with ligand 3.61, a single isomer is formed with an excellent enantiomeric excess [936,937], The same catalyst also provides satisfactory results in the cyclopropanation of alkynes by menthyl diazoacetate [937, 939] or in the intramolecular insertion of diazoesters into C-H bonds [940]. 

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