Helically Chiral Aromatics: The Synthesis of Helicenes by [2 + 2 + 2] Cycloisomerization of π-Electron Systems

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00519391" target="_blank" >RIV/61388963:_____/20:00519391 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/abs/10.1021/acs.accounts.9b00364" target="_blank" >https://pubs.acs.org/doi/abs/10.1021/acs.accounts.9b00364</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.accounts.9b00364" target="_blank" >10.1021/acs.accounts.9b00364</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Helically Chiral Aromatics: The Synthesis of Helicenes by [2 + 2 + 2] Cycloisomerization of π-Electron Systems

Popis výsledku v původním jazyce

Advanced molecular nanocarbons are now in the spotlight reflecting the basic discoveries of fullerenes, carbon nanotubes, and graphene. This research area includes also the chemistry, physics, and nanoscience of nonplanar polycyclic hydrocarbons, many of which exhibit helical chirality, such as iconic helicenes and their congeners. The combination of unique π-electron systems with the chirality phenomenon makes them highly attractive in various fields of science. Helicenes are polyaromatic compounds that are composed of all-angularly annulated benzene units, but other (hetero)cycles can also be embedded into their backbone. Even though they do not contain any stereogenic center, they are inherently chiral owing to the helical shape they adopt. Hexahelicene and higher homologues are conformationally stable within a reasonable range of temperatures and, therefore, can be obtained in an enantiopure form through a racemate resolution or asymmetric synthesis. An amazing array of synthetic methods for their preparation has been developed, but only a few of them have passed the tough scrutiny to be general, robust and practical methods such as traditional photocyclodehydrogenation of diaryl olefins and recently developed transition-metal-catalyzed [2 + 2 + 2] cycloisomerization of π-electron systems, which is discussed in this Account. Alkyne [2 + 2 + 2] cycloisomerization is a highly exergonic process and is therefore suitable for forming the strained helicene backbone, three (or more) cycles of which are closed in a single operation. The typical starting materials are aromatic triynes (optionally cyanodiynes or ynedinitriles) or tetraynes with diynes that undergo intramolecular or intermolecular cyclization, respectively, catalyzed by various complexes mainly of Ni0, CoI, or RhI. Utilizing this synthetic methodology, various [5]-, [6]-, [7]-, [9]-, [11]-, [13]-, [16]-, [17]-, and [19]helicenes or their congeners, including functionalized derivatives, can be effectively prepared. Moreover, asymmetric synthesis (both catalytic and stoichiometric) of nonracemic helicenes has already been demonstrated. It relies on [2 + 2 + 2] cycloisomerization of centrally chiral triynes followed by an asymmetric transformation of the first order (controlled by the 1,3-allylic-type strain) or on enantioselective [2 + 2 + 2] cycloisomerization of alkynes catalyzed by chiral complexes mainly of Ni0 or RhI. Intriguingly, advanced helical architectures were formed such as the longest helicenes (up to oxa[19]helicene by closing 12 rings in a single synthetic operation) or laterally extended helicenes (e.g., pyreno[7]helicenes). Utilizing the aforementioned synthetic methodology, the tailor-made helical molecular nanocarbons are now better accessible to be applied in enantioselective catalysis, chirality sensing, spintronics (based on chirality induced spin selectivity), chiroptics (to produce circularly polarized light emission), organic/molecular electronics, or chiral single molecule devices.

Název v anglickém jazyce

Helically Chiral Aromatics: The Synthesis of Helicenes by [2 + 2 + 2] Cycloisomerization of π-Electron Systems

Popis výsledku anglicky

Advanced molecular nanocarbons are now in the spotlight reflecting the basic discoveries of fullerenes, carbon nanotubes, and graphene. This research area includes also the chemistry, physics, and nanoscience of nonplanar polycyclic hydrocarbons, many of which exhibit helical chirality, such as iconic helicenes and their congeners. The combination of unique π-electron systems with the chirality phenomenon makes them highly attractive in various fields of science. Helicenes are polyaromatic compounds that are composed of all-angularly annulated benzene units, but other (hetero)cycles can also be embedded into their backbone. Even though they do not contain any stereogenic center, they are inherently chiral owing to the helical shape they adopt. Hexahelicene and higher homologues are conformationally stable within a reasonable range of temperatures and, therefore, can be obtained in an enantiopure form through a racemate resolution or asymmetric synthesis. An amazing array of synthetic methods for their preparation has been developed, but only a few of them have passed the tough scrutiny to be general, robust and practical methods such as traditional photocyclodehydrogenation of diaryl olefins and recently developed transition-metal-catalyzed [2 + 2 + 2] cycloisomerization of π-electron systems, which is discussed in this Account. Alkyne [2 + 2 + 2] cycloisomerization is a highly exergonic process and is therefore suitable for forming the strained helicene backbone, three (or more) cycles of which are closed in a single operation. The typical starting materials are aromatic triynes (optionally cyanodiynes or ynedinitriles) or tetraynes with diynes that undergo intramolecular or intermolecular cyclization, respectively, catalyzed by various complexes mainly of Ni0, CoI, or RhI. Utilizing this synthetic methodology, various [5]-, [6]-, [7]-, [9]-, [11]-, [13]-, [16]-, [17]-, and [19]helicenes or their congeners, including functionalized derivatives, can be effectively prepared. Moreover, asymmetric synthesis (both catalytic and stoichiometric) of nonracemic helicenes has already been demonstrated. It relies on [2 + 2 + 2] cycloisomerization of centrally chiral triynes followed by an asymmetric transformation of the first order (controlled by the 1,3-allylic-type strain) or on enantioselective [2 + 2 + 2] cycloisomerization of alkynes catalyzed by chiral complexes mainly of Ni0 or RhI. Intriguingly, advanced helical architectures were formed such as the longest helicenes (up to oxa[19]helicene by closing 12 rings in a single synthetic operation) or laterally extended helicenes (e.g., pyreno[7]helicenes). Utilizing the aforementioned synthetic methodology, the tailor-made helical molecular nanocarbons are now better accessible to be applied in enantioselective catalysis, chirality sensing, spintronics (based on chirality induced spin selectivity), chiroptics (to produce circularly polarized light emission), organic/molecular electronics, or chiral single molecule devices.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA16-08327S" target="_blank" >GA16-08327S: Chirální organicko-anorganické hybridní materiály a jejich využití v nanovědě</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Accounts of Chemical Research

ISSN

0001-4842

e-ISSN

—

Svazek periodika

53

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

15

Strana od-do

144-158

Kód UT WoS článku

000509420300013

EID výsledku v databázi Scopus

2-s2.0-85076689756