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Download fileEnantioselective Construction of a Polyhydroxylated Pyrrolidine Skeleton from 3‑Vinylaziridine-2-carboxylates: Synthesis of (+)-DMDP and a Potential Common Intermediate for (+)-Hyacinthacine A1 and (+)-1-epi-Australine
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posted on 2012-09-21, 00:00 authored by Yukari Kondo, Noriyuki Suzuki, Masato Takahashi, Takuya Kumamoto, Hyuma Masu, Tsutomu IshikawaWe report an enantioselective synthesis of the polyhydroxylated
pyrrolidine alkaloid (+)-DMDP. The key steps in the synthesis were
guanidinium ylide mediated asymmetric aziridination, stereospecific
ring opening of trans-3-vinylaziridine-2-carboxylate
with an oxygen nucleophile, iodine-mediated 5-endo-trig amino cyclization, and Prévost displacement. In addition,
a potential common intermediate for the polyhydroxylated pyrrolizidine
alkaloids (+)-hyacinthacine A1 and (+)-1-epi-australine was synthesized from a diastereoisomeric cis-aziridine coformed in the asymmetric aziridination using the same
strategy. A rationale for the diastereoselectivity observed for the
iodine-mediated amino cyclization reactions is proposed on the basis
of the heats of formation of the products.
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DMDPalkaloidcoformeddiastereoisomericalkaloidspolyhydroxylatedpyrrolidinerationalestrategyguanidinium ylidestereospecific ring openingEnantioselective Constructionenantioselective synthesisHyacinthacinebasispyrrolizidinediastereoselectivityVinylaziridineaziridinationdisplacementformationhyacinthacinePrecyclization reactionstranoxygen nucleophilePolyhydroxylated Pyrrolidine SkeletonSynthesiPotential Common Intermediate