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Synthesis of (−)‐Cubebol by Face‐Selective Platinum‐, Gold‐, or Copper‐Catalyzed Cycloisomerization: Evidence of Chirality Transfer and Mechanistic Insights
Author(s) -
Fehr Charles,
Winter Beat,
Magpantay Iris
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200901292
Subject(s) - cycloisomerization , chirality (physics) , catalysis , chemistry , propargyl , copper , combinatorial chemistry , selectivity , stereochemistry , stereoselectivity , photochemistry , organic chemistry , physics , chiral symmetry breaking , nambu–jona lasinio model , quark , quantum mechanics
We describe in detail a direct, stereoselective synthesis of (−)‐cubebol based on a Pt‐, Au‐, or Cu‐catalyzed cycloisomerization in which control of the configuration of the propargylic center is essential for the facial selectivity. In addition, we show that cycloisomerization reactions of enantioenriched propargyl pivalates occur with substantial chirality transfer. We confirm a mechanism by means of cyclization followed by an [1,2]‐acyl migration for the Pt‐ and the Au‐catalyzed cycloisomerization. So far, no evidence supports that the Cu‐catalyzed cycloisomerization follows the same reaction course.