C(sp<sup>3</sup>)H Activation without a Directing Group: Regioselective Synthesis of <i>N</i>‐Ylide or <i>N</i>‐Heterocyclic Carbene Complexes Controlled by the Choice of Metal and Ligand
抄録
<jats:title>Abstract</jats:title><jats:p><jats:italic>N</jats:italic>‐Ylide complexes of Ir have been generated by C(sp<jats:sup>3</jats:sup>)H activation of α‐pyridinium or α‐imidazolium esters in reactions with [Cp*IrCl<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub> and NaOAc. These reactions are rare examples of C(sp<jats:sup>3</jats:sup>)H activation without a covalent directing group, which—even more unusually—occur α to a carbonyl group. For the reaction of the α‐imidazolium ester [<jats:bold>3</jats:bold>H]Cl, the site selectivity of CH activation could be controlled by the choice of metal and ligand: with [Cp*IrCl<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub> and NaOAc, C(sp<jats:sup>3</jats:sup>)H activation gave the <jats:italic>N</jats:italic>‐ylide complex <jats:bold>4</jats:bold>; in contrast, with Ag<jats:sub>2</jats:sub>O followed by [Cp*IrCl<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub>, C(sp<jats:sup>2</jats:sup>)H activation gave the N‐heterocyclic carbene complex <jats:bold>5</jats:bold>. DFT calculations revealed that the <jats:italic>N</jats:italic>‐ylide complex <jats:bold>4</jats:bold> was the kinetic product of an ambiphilic CH activation. Examination of the computed transition state for the reaction to give <jats:bold>4</jats:bold> indicated that unlike in related reactions, the acetate ligand appears to play the dominant role in CH bond cleavage.</jats:p>
収録刊行物
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- Chemistry – A European Journal
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Chemistry – A European Journal 20 (41), 13203-13209, 2014-08-27
Wiley