Enantioselective synthesis of tripodal cyclophanes and pyridinophanes by intramolecular [2+2+2] cycloaddition

Takanori Shibata; Mayu Miyoshi; Toshifumi Uchiyama; Kohei Endo; Nobuaki Miura; Kenji Monde

doi:10.1016/j.tet.2012.01.046

Enantioselective synthesis of tripodal cyclophanes and pyridinophanes by intramolecular [2+2+2] cycloaddition

Takanori Shibata^*, Mayu Miyoshi, Toshifumi Uchiyama, Kohei Endo, Nobuaki Miura, Kenji Monde

^*Corresponding author for this work

School of Advanced Science and Engineering

Research output: Contribution to journal › Article › peer-review

24 Citations (Scopus)

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	https://doi.org/10.1016/j.tet.2012.01.046
Publication status	Published - 2012 Mar 25

Keywords

Cycloaddition
Cyclophane
Enantioselective
Planar chirality

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tet.2012.01.046

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title = "Enantioselective synthesis of tripodal cyclophanes and pyridinophanes by intramolecular [2+2+2] cycloaddition",

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.",

keywords = "Cycloaddition, Cyclophane, Enantioselective, Planar chirality",

author = "Takanori Shibata and Mayu Miyoshi and Toshifumi Uchiyama and Kohei Endo and Nobuaki Miura and Kenji Monde",

note = "Funding Information: This work was supported by Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan (No. 22350046 ) and the Global COE program {\textquoteleft}Center for Practice Chemical Wisdom{\textquoteright} by MEXT. We also thank Takasago International Corp. for the gift of Cy-BINAP and H 8 -BINAP. ",

year = "2012",

month = mar,

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doi = "10.1016/j.tet.2012.01.046",

language = "English",

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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

N1 - Funding Information: This work was supported by Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan (No. 22350046 ) and the Global COE program ‘Center for Practice Chemical Wisdom’ by MEXT. We also thank Takasago International Corp. for the gift of Cy-BINAP and H 8 -BINAP.

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

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JO - Tetrahedron

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Enantioselective synthesis of tripodal cyclophanes and pyridinophanes by intramolecular [2+2+2] cycloaddition

Abstract

Keywords

ASJC Scopus subject areas

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