Asymmetric photochemical reactions in solution

Inoue, Yoshihisa

doi:10.1021/cr00013a001

Cited by 634 publications

(324 citation statements)

References 105 publications

(143 reference statements)

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“…After stirring for 12 h, the reaction mixture was poured into brine and extracted with tetrahydrofuran. The organic layer was washed with water, dried over anhydrous MgSO 4 and condensed in a rotary evaporator, to yield a crude product. Column chromatography on silica gel with tetrahydrofuran/hexane 1:1 as an eluent and recrystallization in ethanol produced pure 1 as a red solid (0.219 g, yield 35.57% Photoinduced self-assembly of 1.…”

Section: Methodsmentioning

confidence: 99%

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Induction and control of supramolecular chirality by light in self-assembled helical nanostructures

et al. 2015

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Evolution of supramolecular chirality from self-assembly of achiral compounds and control over its handedness is closely related to the evolution of life and development of supramolecular materials with desired handedness. Here we report a system where the entire process of induction, control and locking of supramolecular chirality can be manipulated by light. Combination of triphenylamine and diacetylene moieties in the molecular structure allows photoinduced self-assembly of the molecule into helical aggregates in a chlorinated solvent by visible light and covalent fixation of the aggregate via photopolymerization by ultraviolet light, respectively. By using visible circularly polarized light, the supramolecular chirality of the resulting aggregates is selectively and reversibly controlled by its rotational direction, and the desired supramolecular chirality can be arrested by irradiation with ultraviolet circularly polarized light. This methodology opens a route to ward the formation of supramolecular chiral conducting nanostructures from the self-assembly of achiral molecules.

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Section: Methodsmentioning

confidence: 99%

“…Irradiation with CPL of a racemic mixture of chiral molecules can selectively enrich one enantiomer up to a small extent, called 'symmetry breaking' 3,4 . It has been speculated that this slight chiral bias might have been amplified via autocatalytic reactions or crystallization processes during the evolutionary process 5 , resulting in homochirality.…”

mentioning

confidence: 99%

Induction and control of supramolecular chirality by light in self-assembled helical nanostructures

et al. 2015

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“…At present, there are only a few examples of the influence of chirality on photochemical processes [4,5,6,7,8,9,10,11,12]. The difference in the radical transformation of the (R) and (S) enantiomers of 2-phenylpropionic acid in the reaction with 4-methyl-2-quinolinecarbonitrile was detected using spin chemistry methods [13].…”

Section: Introductionmentioning

confidence: 99%

Spin effects in intramolecular electron transfer in naproxen-N-methylpyrrolidine dyad

Magin

Polyakov

Khramtsova

et al. 2011

Chemical Physics Letters

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The intramolecular electron transfer in the naproxen-N-methyl-pyrrolidine dyad has been investigated by spin chemistry methods. The existence of CIDNP in a high magnetic field points to electron transfer as a possible mechanism of the quenching of the excited state of a dyad.However, the failure to detect magnetic field effects on triplet yield makes us conclude that this quenching mechanism is not the only one. The observation of CIDNP effects in the dyad in the media of low polarity and the short risetime of triplet state formation indicate a potential role of exciplex in the quenching of the excited state of the dyad.

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“…3,4 Target materials include small molecules, polymers and supramolecular ensembles. Since chiral polymers find a wide range of applications, facile methods of synthesis using CPL are important.…”

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confidence: 99%

Chirality induction using circularly polarized light into a branched oligofluorene derivative in the presence of an achiral aid molecule

2016

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Chirality induction to a uniform, star-shaped fluorene oligomer with a central truxene moiety (T3) was achieved using circularly polarised light in the presence of achiral fluorene or phenanthrene. Induction to T3 alone was difficult, suggesting that close chain packing realised through interactions of T3 with small molecules plays a role in chirality induciton.Circularly polarised light (CPL) was proposed to be a source of chirality for the synthesis of asymmetric organic molecules for the first time in 1874, 1,2 and various experimental examples of CPL-based chiral synthesis have been reported thereafter. 3,4Target materials include small molecules, polymers and supramolecular ensembles. Since chiral polymers find a wide range of applications, facile methods of synthesis using CPL are important. 5 As for CPL-based chiral polymer preparation, a polymethacrylate bearing a side chain containing an azobenzene moiety was for the first time made optically active using CPL; 6 polymers having azobenzene moieties buried in the main-chain have also been studied. 7 We have recently reported a preferred-handed helix formation of linear poly(9,9-di-n-octylfluoren-2,7-diyl) (PDOF) using CPL as a chirality source, where the twist bias around the single bonds connecting the aromatic groups was controlled by chirality of light.8,9a PDOF became optically active in a thin film form on CPL irradiation and exhibited intense circular dichroism (CD) bands. The optical activity of PDOF arises from a 5/1-helical conformation of the polymer generated from a random conformation as disclosed through metadynamics simulation of stereomutation of the polymer chain. 9Through the simulations, inter-chain interactions as well as chain-tosubstrate interactions were found to be important in chirality induction. The conformational transformation is triggered by a "twist-coplanar" transition of the Ar-Ar unit on photoexcitation. 10 Selective photoexcitation of a right-or lefthanded twist modifies a chiral twist into an achiral coplanar conformation which can be deactivated into both right-and left-handed twists, leading to a decrease in population of the selectively excited twist where a preferred-handed twist (helix) is formed. 8,9a,11Herein, we report chirality induction to a monodisperse, welldefined, star-shaped oligofluorene with a central truxene core and terfluorene arms (T3, Scheme 1). 12 T3 has a higher luminescence quantum yield than linear polymer systems and also has a high nonlinear absorption coefficient. 12b On the basis of these characters, T3 is a promising candidate for photo electronic material, and addition of chirality would widen its range of application. Chirality induction to T3, however, is a challenge since the solid-state form of T3 does not have close packing of chains due to its branched structure, while chain-tochain interactions have been found to be important in chirality induction to linear PDOF 8,9a .Scheme 1. Structures of compounds used in this work.

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Asymmetric photochemical reactions in solution

Cited by 634 publications

References 105 publications

Induction and control of supramolecular chirality by light in self-assembled helical nanostructures

Induction and control of supramolecular chirality by light in self-assembled helical nanostructures

Spin effects in intramolecular electron transfer in naproxen-N-methylpyrrolidine dyad

Chirality induction using circularly polarized light into a branched oligofluorene derivative in the presence of an achiral aid molecule

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