Bruce D. Harris

Synthetic studies of didemnins. II. Approaches to statine diastereomers

Abstract A short and efficient route to (3S,4R)-statine has been developed in connection with synthetic studies toward didemnins A,B and C.

Synthetic studies of didemnins. III : Syntheses of statine and isostatine stereoisomers

Abstract The stereoselectivity of the reduction of β-keto ester precursors leading to several stereoisomers of statine and isostatine was investigated. As a result, a short and highly stereoselective route to the isomar of isostatine found in the didemnins, (3S,4R,5S)-isostaline, was devised.

Synthetic studies of the detoxin complex. I. total synthesis of (-) detoxinine

A total synthesis of (-) detoxinine (1), the parent amino acid of the detoxin complex is reported. Two different routes to key intermediate 8a were developed: one from an acyclic precursor and the other from L-proline. The elaboration of 8a to 1 employed a stereoselective aldol condensation.

Synthesis of 3S-Pyrrolidinol from L-Glutamic Acid

Abstract A practical synthesis of 3S-pyrrolidinol and derivatives from L-glutamic acid is described.

Synthetic studies of didemnins. IV. Synthesis of the macrocycle

Abstract A stereocontrolled route to the 23-membered macrocycle found in the didemnins is described.

HIGH 1,6 DIASTEREOSELECTIVITY IN THE HYDRIDE REDUCTION OF AN ACYCLIC KETONE SUBSTRATE VIA BICYCLIC CHELATION CONTROL

Abstract Reduction of acyclic e-hydroxy ketone 3 with R -Alpine-Hydride ® in methylene chloride provided a strong preponderance of the anti diastereomer of 4 ( anti : syn = 12:1). This impressive 1,6 stereoselectivity is attributed to bicyclic chelation control of hydride addition.