008-基元反应(插入)11.07.pptxVIP

;氧化加成和还原消除反应; A = B为C = C、 R’RC = O、C = N等。 :A – B为一氧化碳:C O、异氰 :C N – R、卡宾:CR2等。;Oxidative addition/reductive elimination processes are central to a vast array of synthetically useful organometallic reactions (eg. “Heck” reaction), and occur because of the ability of transition metals to exist in several different oxidation states, in contrast to nontransition metal compounds, which usually have closed shell configurations. In fact, it is the facile shuttling between oxidation states that makes transition metals so useful in organic synthesis.;;;;氧化加成和还原消除是以Vaska(1968)配合物IrCl(CO)(PPh3)2和Wilkinson配合物RhCl(PPh3)3的发现及反应性研究开始的，对了解催化反应机理非常重要。;Note that many of these result in the formation of M-H and M-C bonds, and in the “activation” of a range of organic substrates.;;Concerted oxidative additions are best known for nonpolar substrates, eg. H2, and C-H bonds.;Oxidative addition via SN2-type processes is most often observed with strongly nucleophilic, low valent metals and classic SN2 substrates such as organic halides and tosylates.;Collman’s reagent, Na2Fe(CO)4, a very potent nucleophile, reacts with RX via SN2.;Competing radical chain mechanism for oxidative addition.Traces of air sometimes promote the reaction of complexes which normally require strict exclusion of air, and serves as a warning that the mechanism by which a reaction proceeds may be a function of the care with which it is carried out.;Ni catalyzed coupling of aryl halides to biaryls, which was originally thought to proceed by two sequential two-electron oxidative additions. However, careful studies showed this was not the case. Rather, a complicated radical chain process involving Ni(I) to Ni(III) oxidative addition is the true course of the reaction.;;;;;;;;;;;;;;;;;;;氧化加成和还原消除反应;;Reductive elimination is the reverse of oxidative addition and is usually the last step of many catalytic processes. It is exceptionally important for organic synthetic applications because it is the major way in w