Abstract
An enantioselective intramolecular [2+2+2] cycloaddition of 2-aminophenol-tethered triynes and diyne-nitriles proceeded using the chiral Rh catalysts, and tripodal cyclophanes and pyridinophanes with a long ansa chain (up to [16]pyridinophane) were obtained in acceptable yield with high to almost perfect ee. In the reaction of triynes, we elucidated that the oxygen atom at the alkyne terminus is essential for the excellent enantioselectivity. For the construction of cage-type molecule, the choice of rigid tether, which connects 1,6-diyne moiety with a side carbon chain having alkyne or cyano group on its terminus, was important, and 8-amino-2-naphthol moiety was also a preferable tether.
| Original language | English |
|---|---|
| Pages (from-to) | 2679-2686 |
| Number of pages | 8 |
| Journal | Tetrahedron |
| Volume | 68 |
| Issue number | 12 |
| DOIs | |
| Publication status | Published - 2012 Mar 25 |
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Keywords
- Cycloaddition
- Cyclophane
- Enantioselective
- Planar chirality
ASJC Scopus subject areas
- Biochemistry
- Organic Chemistry
- Drug Discovery
Cite this
Enantioselective synthesis of tripodal cyclophanes and pyridinophanes by intramolecular [2+2+2] cycloaddition. / Shibata, Takanori; Miyoshi, Mayu; Uchiyama, Toshifumi; Endo, Kohei; Miura, Nobuaki; Monde, Kenji.
In: Tetrahedron, Vol. 68, No. 12, 25.03.2012, p. 2679-2686.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Enantioselective synthesis of tripodal cyclophanes and pyridinophanes by intramolecular [2+2+2] cycloaddition
AU - Shibata, Takanori
AU - Miyoshi, Mayu
AU - Uchiyama, Toshifumi
AU - Endo, Kohei
AU - Miura, Nobuaki
AU - Monde, Kenji
PY - 2012/3/25
Y1 - 2012/3/25
N2 - An enantioselective intramolecular [2+2+2] cycloaddition of 2-aminophenol-tethered triynes and diyne-nitriles proceeded using the chiral Rh catalysts, and tripodal cyclophanes and pyridinophanes with a long ansa chain (up to [16]pyridinophane) were obtained in acceptable yield with high to almost perfect ee. In the reaction of triynes, we elucidated that the oxygen atom at the alkyne terminus is essential for the excellent enantioselectivity. For the construction of cage-type molecule, the choice of rigid tether, which connects 1,6-diyne moiety with a side carbon chain having alkyne or cyano group on its terminus, was important, and 8-amino-2-naphthol moiety was also a preferable tether.
AB - An enantioselective intramolecular [2+2+2] cycloaddition of 2-aminophenol-tethered triynes and diyne-nitriles proceeded using the chiral Rh catalysts, and tripodal cyclophanes and pyridinophanes with a long ansa chain (up to [16]pyridinophane) were obtained in acceptable yield with high to almost perfect ee. In the reaction of triynes, we elucidated that the oxygen atom at the alkyne terminus is essential for the excellent enantioselectivity. For the construction of cage-type molecule, the choice of rigid tether, which connects 1,6-diyne moiety with a side carbon chain having alkyne or cyano group on its terminus, was important, and 8-amino-2-naphthol moiety was also a preferable tether.
KW - Cycloaddition
KW - Cyclophane
KW - Enantioselective
KW - Planar chirality
UR - http://www.scopus.com/inward/record.url?scp=84857631725&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84857631725&partnerID=8YFLogxK
U2 - 10.1016/j.tet.2012.01.046
DO - 10.1016/j.tet.2012.01.046
M3 - Article
AN - SCOPUS:84857631725
VL - 68
SP - 2679
EP - 2686
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 12
ER -