Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 264-269 |
| Number of pages | 6 |
| Journal | Chemistry - A European Journal |
| Volume | 19 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 2013 Jan 2 |
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Keywords
- allylic compounds
- chirality
- morphine
- sigmatropic rearrangement
- total synthesis
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Synthesis of (-)-morphine : Application of sequential claisen/claisen rearrangement of an allylic vicinal diol. / Ichiki, Masato; Tanimoto, Hiroki; Miwa, Shohei; Saito, Ryosuke; Satou, Takaaki; Chida, Noritaka.
In: Chemistry - A European Journal, Vol. 19, No. 1, 02.01.2013, p. 264-269.Research output: Contribution to journal › Article
}
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 - Satou, 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
UR - http://www.scopus.com/inward/record.url?scp=84871580288&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84871580288&partnerID=8YFLogxK
U2 - 10.1002/chem.201203284
DO - 10.1002/chem.201203284
M3 - Article
VL - 19
SP - 264
EP - 269
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 1
ER -