Reagents as nucleophiles

Classify these reagents as nucleophiles or electrophiles H OH H2O OAc (acetate) CH3NH2 HPOf AICI3 OOH. ... 

Examples involving the use of organomercury reagents as nucleophiles in aqueous media are also known. Bergstrom studied the synthesis of C-5-substituted pyrimidine nucleosides in aqueous media via a mercurated intermediate using Li2PdCl4 as a catalyst (Eq. 6.42).136... 

Feringa and co-workers described the tandem addition-aldol cyclization protocol leading to the formation of 6,6-, 6,7-, and 6,8-annulated bicyclic systems (Scheme 68).39 Using Cu(n)-29 as catalyst and functionalized organozinc reagents as nucleophiles, the conjugate addition reaction followed by aldol cyclization can offer highly enantioselec-tive annulation products (up to 98% ee). This method can be used in the synthesis of carbocyclic compounds, such as steroids, terpenes, and other natural products. 

The use of organometallic reagents as nucleophiles towards carbonyl compounds is also synthetically important, since it results in the formation of new C-C bonds, building up the size and complexity of the molecule. For carbon to act as a nucleophile, we require a negative charge on carbon, i.e. a carbanion or equivalent. Although there are a variety... 

Miiller and Nury examined aziridine ring opening using Grignard reagents as nucleophiles. They found that the reaction proceeds in moderate selectivities in the presence of copper catalysts such as 69 ... 

Well see many more uses of Grignard reagents as nucleophiles in later chapters. 

The reactions of nitriles with water, hydride, and oiganometallic reagents as nucleophiles are as follows ... 

The stereocontrolled synthesis of alkenes and the use of vinyl- and alkyl-aluminum and -aluminate reagents as nucleophiles has been described above. In addition, the aluminum reagents are also useful in diene synthesis, in reactions with enones and epoxides, and in cyclizations. 

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