Carbonates nucleophilic addition

Until then, only heterogeneous catalyst had been successful. However, in the mid-1980s, the work of Ito et al. led to an outstanding discovery in a catalytic asymmetric aldol reaction. In this case, enantioselectivity was given by a chiral ferrocene diphosphine ligand, with a carbon nucleophile addition to a carbonyl... 

The addition of oxygen and chloride nucleophiles to dienes transiently activated by catalytic Pd is a practical process for production of 1,4-disubstituted 2-alkenes from 1,3-dienes however, it is not useful with carbon nucleophiles. Examples of carbon nucleophile addition to Fe° and Mo complexes show useful selectivity, but only in stoichiometric processes, and few applications have appeared. 

Barluenga, J., Florez, J., Fananas, F. J. Carbon nucleophile addition to sp -unsaturated Fischer carbene complexes. J. Organomet. Chem. 2001,624,5-17. 

The first organocatalytic asymmetric carbon nucleophilic addition to enals was reported by MacMillan in 2001 [15]. MacMillan reported the first Friedel-Craft alkylation between N-substituted pyrroles and enals promoted by catalyst 7. The reaction renders the final compounds in good yields and enantioselectivities (Scheme 33.4). 

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