Synthesis of (-)-longithorone A: Using organic synthesis to probe a proposed biosynthesis

We present a full report of our enantioselective synthesis of -longithorone A

Carl A. Morales; Mark E. Layton; Matthew D. Shair

2004

Scholarcy highlights

  • We present a full report of our enantioselective synthesis of-longithorone A
  • In this paper we present a full description of our synthesis, findings that elucidate the timing of the Diels–Alder reactions proposed for the biosynthesis of 1, and additional examples of ene–yne metathesis macrocyclization demonstrating its usefulness in forming macrocyclic 1,3-disubstituted dienes
  • Materials and Methods Details describing chemical synthesis, general procedures, instrumentation, molecular modeling, optimization of ene–yne metathesis macrocyclization conditions, and substrate tables for macrocyclizations and enantioselective vinylzinc additions can be found in Supporting Materials and Methods, which is published as supporting information on the PNAS web site
  • Having demonstrated that we could synthesize 1,3-disubstituted dienes from an ene– yne metathesis macrocyclization and use them in Diels–Alder reactions, we focused our efforts toward the synthesis of 1
  • The synthesis suggests that in the biosynthesis of 1 the intermolecular Diels–Alder reaction occurs before the transannular Diels–Alder reaction because of the low reactivity of enal 4.-Paracyclophanes were synthesized in the ene–yne metathesis macrocyclization
  • Secondary benzylic alcohols were synthesized in high yield by enantioselective vinylzinc additions to electron-rich benzaldehydes
  • C.A.M. and M.E.L. acknowledge the National Science Foundation for predoctoral fellowships

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