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A Tandem, Nitroalkene Conjugate Addition/[3+2] Cycloaddition Approach to the Synthesis of the Pentacyclic Core of (±)‐Scandine
Author(s) -
Denmark Scott E.,
Cottell Jeromy J.
Publication year - 2006
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200600301
Subject(s) - chemistry , nitroalkene , aldehyde , intramolecular force , stereocenter , cycloaddition , stereochemistry , reductive amination , allylic rearrangement , conjugate , enantioselective synthesis , organic chemistry , catalysis , mathematical analysis , mathematics
The complete pentacyclic core of the melodinus alkaloid scandine has been synthesized. The synthetic strategy features two key steps: (1) a tandem nitroalkene conjugate addition/[3+2] cycloaddition of the resulting silyl nitronate and (2) an intramolecular Heck reaction of an aryl iodide with a γ‐disubstituted allylic alcohol which set a highly congested, quaternary stereogenic center with the concomitant formation of an aldehyde. Intramolecular reductive amination with this aldehyde completed the pentacyclic core.