Organometallics conjugate acceptors

P.-T. Wu, T. Bull, E S. Kim, C. K. Luscombe, S. A. Jenekhe, Organometallic Donor-Acceptor Conjugated Polymer Semiconductors Tunable Optical, Electrochemical, Charge Transport, and Photovoltaic Properties. Macromolecules 2009,42, 671-681. 

The conjugate addition of organometallic reagents to a./i-unsaturated compounds is one of the basic methods in our repertoire for the construction of carbon-carbon bonds. These addition reactions have been used as key steps in the synthesis of numerous biologically active compounds, and show a broad scope due to the large variety of donor and acceptor compounds that can be employed. It is evident that a tremendous effort has been devoted over the last three decades to develop asymmetric variants of this reaction. ... 

Two basic approaches have been taken. The first consists in grafting organometallic donor and acceptor groups, such as ferrocene [as in [84] (Calabrese et al, 1991)] ruthenium derivatives [as in [83] (Whittall et al, 1996)] and tungsten carbonyl, instead of their organic counterparts on tt-conjugated chains. Quite successful in this respect, although not truly org nometallic, are zwitterions based on borate donors and ammonium acceptors [86] (Lambert et ah, 1996) and Lewis acid complexation as in [85] (Kammler et al, 1996). 

Many examples of selective conjugate additions of organometallic reagents to chiral substrates have been described. The chiral residue can be introduced either on the electron-withdrawing group or on the carbon skeleton of the acceptor. 

The term Michael addition has been used to describe 1,4- (conjugate) additions of a variety of nucleophiles including organometallics, heteroatom nucleophiles such as sulfides and amines, enolates, and allylic organometals to so-called Michael acceptors such as a,p-unsaturated aldehydes, ketones, esters, nitriles, sulfoxides, and nitro compounds. Here, the term is restricted to the classical Michael reaction, which employs resonance-stabilized anions such as enolates and azaenolates, but a few examples of enamines are also included because of the close mechanistic similarities. 

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