Abstract
A catalytic asymmetric formal synthesis of 4-demethoxydaunomycin (3) was achieved using a catalytic asymmetric ring opening reaction of meso-epoxide 9 as a key step. The epoxide opening reaction was promoted by 10 mol% of Pr-(R)-BINOL-Ph3P=O complex to give the β-amino alcohol 11 in 80% yield with 65% enantiomeric excess (ee). Single recrystallization enhanced the enantiomeric purity of the β-amino alcohol 11 to 95% ee. The β-amino alcohol 11 was then converted to the known key intermediate 6 through several steps, including a methylation, Hofmann elimination, an oxymercuration, and addition of an ethynyl group in a highly diastereoselective manner.
| Original language | English |
|---|---|
| Pages (from-to) | 75-82 |
| Number of pages | 8 |
| Journal | Tetrahedron |
| Volume | 58 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - Jan 1 2002 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Biochemistry
- Drug Discovery
- Organic Chemistry
Cite this
An enantioselective formal synthesis of 4-demethoxydaunomycin using the catalytic asymmetric ring opening reaction of meso-epoxide with p-anisidine. / Sekine, Akihiro; Ohshima, Takashi; Shibasaki, Masakatsu.
In: Tetrahedron, Vol. 58, No. 1, 01.01.2002, p. 75-82.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - An enantioselective formal synthesis of 4-demethoxydaunomycin using the catalytic asymmetric ring opening reaction of meso-epoxide with p-anisidine
AU - Sekine, Akihiro
AU - Ohshima, Takashi
AU - Shibasaki, Masakatsu
PY - 2002/1/1
Y1 - 2002/1/1
N2 - A catalytic asymmetric formal synthesis of 4-demethoxydaunomycin (3) was achieved using a catalytic asymmetric ring opening reaction of meso-epoxide 9 as a key step. The epoxide opening reaction was promoted by 10 mol% of Pr-(R)-BINOL-Ph3P=O complex to give the β-amino alcohol 11 in 80% yield with 65% enantiomeric excess (ee). Single recrystallization enhanced the enantiomeric purity of the β-amino alcohol 11 to 95% ee. The β-amino alcohol 11 was then converted to the known key intermediate 6 through several steps, including a methylation, Hofmann elimination, an oxymercuration, and addition of an ethynyl group in a highly diastereoselective manner.
AB - A catalytic asymmetric formal synthesis of 4-demethoxydaunomycin (3) was achieved using a catalytic asymmetric ring opening reaction of meso-epoxide 9 as a key step. The epoxide opening reaction was promoted by 10 mol% of Pr-(R)-BINOL-Ph3P=O complex to give the β-amino alcohol 11 in 80% yield with 65% enantiomeric excess (ee). Single recrystallization enhanced the enantiomeric purity of the β-amino alcohol 11 to 95% ee. The β-amino alcohol 11 was then converted to the known key intermediate 6 through several steps, including a methylation, Hofmann elimination, an oxymercuration, and addition of an ethynyl group in a highly diastereoselective manner.
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UR - http://www.scopus.com/inward/citedby.url?scp=0036135096&partnerID=8YFLogxK
U2 - 10.1016/S0040-4020(01)01088-2
DO - 10.1016/S0040-4020(01)01088-2
M3 - Article
VL - 58
SP - 75
EP - 82
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 1
ER -