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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Veröffentlicht in:	Angewandte Chemie International Edition Jg. 61; H. 15; S. e202200800 - n/a
Hauptverfasser:	Nogami, Juntaro, Nagashima, Yuki, Sugiyama, Haruki, Miyamoto, Kazunori, Tanaka, Yusuke, Uekusa, Hidehiro, Muranaka, Atsuya, Uchiyama, Masanobu, Tanaka, Ken
Format:	Journal Article
Sprache:	Englisch
Veröffentlicht:	WEINHEIM Wiley 04.04.2022 Wiley Subscription Services, Inc
Ausgabe:	International ed. in English
Schlagworte:	[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
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Zusammenfassung:	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.
Bibliographie:	KAKEN ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23
ISSN:	1433-7851 1521-3773 1521-3773
DOI:	10.1002/anie.202200800