Synthesis of Cyclophenacene‐ and Chiral‐Type Cyclophenylene‐Naphthylene Belts

We report the synthesis of a [20]cyclophenacene‐type cyclophenylene‐naphthylene (CPN) belt and the enantioselective synthesis of chiral‐type CPN belts (up to >99 % ee) by the cationic rhodium(I)‐catalyzed intramolecular [2+2+2] cycloaddition of naphthalene‐embedded cyclic polyynes. The synthesis...

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Bibliographic Details
Published in:Angewandte Chemie International Edition Vol. 61; no. 15; pp. e202200800 - n/a
Main Authors: Nogami, Juntaro, Nagashima, Yuki, Sugiyama, Haruki, Miyamoto, Kazunori, Tanaka, Yusuke, Uekusa, Hidehiro, Muranaka, Atsuya, Uchiyama, Masanobu, Tanaka, Ken
Format: Journal Article
Language:English
Published: WEINHEIM Wiley 04.04.2022
Wiley Subscription Services, Inc
Edition:International ed. in English
Subjects:
[2+2+2] Cycloaddition
Anisotropy
Belts
Chemistry
Chemistry, Multidisciplinary
Circular dichroism
Circular polarization
Crystallography
Cycloaddition
Cyclophenylene-Naphthylene Belts
DFT Calculations
Dichroism
Enantiomers
Naphthalene
Physical Sciences
Planar Chirality
Rhodium
Science & Technology
Synthesis
Cyclophenylene-Naphthylene Belts
DESIGN
CARBON
[2+2+2] Cycloaddition
CATALYZED 2+2+2 CYCLOADDITION
MOLECULES
Rhodium
CYCLOPARAPHENYLENES
GROWTH
SYSTEMS
DFT Calculations
Planar Chirality
CHEMICAL-SYNTHESIS
CYCLOTRIMERIZATION
ISSN:1433-7851, 1521-3773, 1521-3773
Online Access:Get full text
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Summary:We report the synthesis of a [20]cyclophenacene‐type cyclophenylene‐naphthylene (CPN) belt and the enantioselective synthesis of chiral‐type CPN belts (up to >99 % ee) by the cationic rhodium(I)‐catalyzed intramolecular [2+2+2] cycloaddition of naphthalene‐embedded cyclic polyynes. The synthesis of a depth‐expanded CPN belt was also attempted, but the final intramolecular [2+2+2] cycloaddition was unsuccessful. Theoretical calculations clarified that the reactivity depends on the stability of the transition state in the initial oxidative cycloaddition step which is subject to molecular strain. The cylindrical structures of these CPN belts were confirmed by X‐ray crystallographic analyses. As a result of π‐extension through the introduction of naphthalenes in the chiral‐type CPN belts, the anisotropy dissymmetry factors of electronic circular dichroism and circularly polarized luminescence are amplified compared with the corresponding zigzag‐type chiral cyclophenylene belts. The synthesis of a [20]cyclophenacene‐type cyclophenylene‐naphthylene (CPN) belt and the enantioselective synthesis of chiral‐type CPN belts have been achieved by the cationic rhodium(I)‐catalyzed intramolecular [2+2+2] cycloaddition of naphthalene‐embedded cyclic polyynes. However, the synthesis of a depth‐expanded CPN belt was unsuccessful. Theoretical calculations clarified that the reactivity depends on the stability of the transition state which is subject to ring strain.
Bibliography:KAKEN
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202200800