Complexity-Building Transformations of Silyl Glyoxylates

Silyl glyoxylates are reagents used for the geminal difunctionalization of a glycolic acid junction with nucleophilic and electrophilic species. The research summarized herein describes the development of new reactions that utilize silyl glyoxylates to generate multiple C-C bonds and stereogenic centers. Significant results include: (1) completion of the synthesis of (+)-zaragozic acid C; (2) development of a tandem Brook/Ireland Claisen rearrangement for the synthesis of functionalized a,b-unsaturated glycolic acids; (3) development of a nitrile-oxide cycloaddition for the synthesis of 3,4-disubstituted isoxazoles; (4) development of a three component glycolate Michael reaction; (5) application of the glycolate Michael reaction to the synthesis of (+)-trachyspic acid dimethyl ester