Metal dienolates

Enolates may be derived from a,/l-unsaturated ketones 16 by base-catalyzed proton abstraction. Under kinetic control the a -proton is abstracted and a cross-conjugated metal dienolate is formed, whereas under thermodynamic conditions the extended dienolate is the major product3,, l. Successful alkylations of dienolates derived from cyclic a,/l-unsaturated ketones have been performed (see Section 1.1.1.3.1.1.2.1.). The related a,/ -unsaturated ester systems have also been investigated22-24. Open-chain structures 16 pose a rather complicated... 

As shown in Scheme 49, the cyclohexylimine of 10-methyl-l(9)-octalin-2-one has been methylated at C-3 via the kinetically formed cross-conjugated dienamine anion (95) or monomethylated at C-1 via the thermodynamically more stable extended anion (96). Steroidal and simpler enones have also been monoalkylated at the a-position via their corresponding hetero- or homo-annular extended dienamine anions. Likewise, a-alkylations are the rule for liAiated a,3-unsaturated aldimines. The thermodynamically controlled procedure for the synthesis of a-methyl a,3-unsaturated ketones is a vast improvement over conventional methodology using extended metal dienolates where a,a-dimethylation is a severe... 

Scheme 5.1 Ambident reaction profile of a metal dienolate [2, 3].

The catalytic, enantioselective, vinylogous Mannich reaction has recently emerged as a very powerful tool in organic synthesis for the assembly of highly functionalized and optically enriched 6 amino carbonyl compounds. Two distinctly different strategies have been developed. The first approach calls for the reaction of preformed silyl dienolates as latent metal dienolates that react in a chiral Lewis acid or Bronsted acid catalyzed Mukaiyama type reaction with imines. Alternatively, unmodified CH acidic substrates such as a,a dicyanoalkenes or 7 butenolides were used in vinylo gous Mannich reactions that upon deprotonation with a basic residue in the catalytic system generate chiral dienolates in situ. 

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