Marine natural products, syntheses including

Boron trifluoride etherate promotes the fWt/a-selcctivc oxacyclization of polyepoxides derived from various acyclic terpenoid polyalkenes, including geraniol, farnesol, and geranylgeraniol, providing an efficient and stereoselective synthesis of substituted oxepanes and fused polyoxepanes. The oxacyclization transformations may mimic ringforming steps in the biosynthesis of trans-syn-trans-fused polycyclic ether marine natural products <2002JOC2515>. 

Additional examples where chloroacetates from acyclic dienes have been used include the synthesis of pentadienylamines [96], dienesulfones [97], c-methylenecyclopentenones [98], marine natural products [99], and the carpenter bee pheromone [82]. Some additional Synthetic applications of the chloroacetoxylation of cyclic dienes are given in Refs. [100-104]. Chloroacetoxylation was also used to prepare a number of starting materials for the intramolecular reactions discussed in this chapter. 

Chris Diaper received his BSc in chemistry in 1996 from the University of Bradford, UK and his PhD in 2000 from the University of Sheffield under the supervision of Dr Alan Spivey. After postdoctoral work at the University of Nottingham with Prof Gerry Pattenden he moved to his current position as a postdoctoral fellow at the University of Alberta, Canada working with Prof John Vederas. His research interests include the development of germanium based linkers for solid-phase sjmthesis, the total synthesis of marine natural products and mechanistic aspects of the diaminopimelate (DAP) biosynthetic pathway. 

A further application of the carbonylation strategy for construction of 2,3-cis substituted tetrahydrofuran derivatives is shown in Scheme 15.23. Nesbitt and McErlean reported on the synthesis of C19 lipid diols, the enantiomers of the anthelmintic marine natural products. Key steps in the divergent synthesis include a syn selective epoxidation of a homoallylic alcohol, a one-pot alkoxypalladation-lactonization reaction sequence, and diethyl azodicarboxy-late promoted Mitsunobu inversion. 

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