TY - JOUR
T1 - Synthesis of (-)-morphine
T2 - Application of sequential claisen/claisen rearrangement of an allylic vicinal diol
AU - Ichiki, Masato
AU - Tanimoto, Hiroki
AU - Miwa, Shohei
AU - Saito, Ryosuke
AU - Sato, Takaaki
AU - Chida, Noritaka
PY - 2013/1/2
Y1 - 2013/1/2
N2 - A detailed exploration of the synthesis of (-)-morphine based on sequential [3,3]-sigmatropic rearrangements is described. The sequential Claisen/Claisen rearrangements of an allylic vicinal diol resulted in the stereoselective formation of the two contiguous carbon centers, including a sterically encumbered quaternary carbon, in a single operation. The two ethyl esters generated in this reaction were successfully differentiated during a subsequent Friedel-Crafts-type cyclization. The (-)-morphine double bond was introduced at a late stage in our first-generation synthesis, but was formed at an earlier stage in the second-generation synthesis, resulting in a more efficient route to the end product.
AB - A detailed exploration of the synthesis of (-)-morphine based on sequential [3,3]-sigmatropic rearrangements is described. The sequential Claisen/Claisen rearrangements of an allylic vicinal diol resulted in the stereoselective formation of the two contiguous carbon centers, including a sterically encumbered quaternary carbon, in a single operation. The two ethyl esters generated in this reaction were successfully differentiated during a subsequent Friedel-Crafts-type cyclization. The (-)-morphine double bond was introduced at a late stage in our first-generation synthesis, but was formed at an earlier stage in the second-generation synthesis, resulting in a more efficient route to the end product.
KW - allylic compounds
KW - chirality
KW - morphine
KW - sigmatropic rearrangement
KW - total synthesis
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U2 - 10.1002/chem.201203284
DO - 10.1002/chem.201203284
M3 - Article
C2 - 23180383
AN - SCOPUS:84871580288
SN - 0947-6539
VL - 19
SP - 264
EP - 269
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 1
ER -